Photosensitive heat-resistant polymer having hydroxyphenyl group for forming a patterned image

A photosensitive polymer containing a repeating unit represented by the following formula (I) and having a logarithmic viscosity number of from 0.1 to 5 dl/g as measured in a solvent at a temperature of 30.degree..+-.0.01.degree. C. at a concentration of 0.5 g/dl: ##STR1## (wherein R.sup.1 is a trivalent or tetravalent carbocyclic aromatic group or heterocyclic group, R.sup.2 is an aliphatic group having at least two carbon atoms, an alicyclic group, an aromatic aliphatic group, a carbocyclic aromatic group, a heterocyclic group or a polysiloxane group, R.sup.3 is a divalent organic group, R.sup.4 is ##STR2## a hydrogen atom or a monovalent organic group, R.sup.5 is a hydrogen atom or a monovalent organic group, m is independently 1 or 2, n is independently 0 or 1, and m and n meet 1.ltoreq.m+n.ltoreq.2); a method for preparing the above-mentioned photosensitive polymer; a photosensitive polymer composition containing the above-mentioned photosensitive polymer; and a method for preparing a poly(amide)imide film.

BACKGROUND OF THE INVENTION 
(i) Field of the Invention 
The present invention relates to a novel photosensitive heat-resistant 
polymer and a method for preparing the same. More specifically, it relates 
to a novel high-sensitivity photosensitive poly(amide)imide precursor 
having an excellent shelf stability, a method for preparing the same, a 
photosensitive polymer composition containing the same, and a method for 
forming a patterned poly(amide)imide film by the use of the same. 
(ii) Description of the Related Art 
Photosensitive polyimides which are heat-resistant photosensitive materials 
have been widely used as insulating films and passivation films for 
semiconductors, but these polyimides have various problems. 
For example, Japanese Patent Application Laid-open No. 54-145794 suggests a 
method for mixing a compound containing a double bond and an amino group 
or its quaternary salt with a polyamic acid, but the change in the 
viscosity of the resultant solution inconveniently increases with time, 
since the compound containing a large amount of the amino group or its 
quaternary salt is added to the unstable polyamic acid solution. Japanese 
Patent Application Laid-open Nos. 55-45746 and 60-100143 suggest methods 
for reacting an unsaturated epoxy compound or an isocyanate compound 
having a double bond with the carboxyl group of various polyamic acids. 
However, when the photosensitive unsaturated group-containing compound is 
reacted with the carboxyl group of the polyamic acid, a part of the 
polyamic acid, for example, decomposes, so that the viscosity of the 
solution changes inconveniently. In Japanese Patent Application 
Publication No. 55-41422, there is suggested a polymer obtained by 
introducing an active functional group such as a double bond into the 
ester side chain of the polyamic acid, but when an acid chloride is 
reacted with a diamine, the chloride remains as an impurity, and the 
removal of this impurity is troublesome. Furthermore, Japanese Patent 
Application Laid-open No. 60-6729 suggests that a diamine having a double 
bond is previously synthesized and a polyimide is then synthesized by 
using the diamine, but a process for introducing the photosensitive 
functional group is intricate and a large cost is required. 
As is apparent from the foregoing, conventional techniques have various 
problems, and it is desired to develop a photosensitive material by which 
the above-mentioned problems can be solved. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a novel photosensitive 
poly(amide)imide precursor having an excellent shelf stability and a good 
sensitivity, containing less impurities, and permitting the same to be 
easily manufactured; a method for preparing the same; a photosensitive 
polymer composition containing the same; and a method for forming a 
patterned poly(amide)imide film by using the same. 
The first aspect of the present invention is directed to a photosensitive 
polymer containing a repeating unit represented by the following formula 
(I) and having a logarithmic viscosity number of from 0.1 to 5 dl/g as 
measured in a solvent at a temperature of 30.degree..+-.0.01.degree. C. at 
a concentration of 0.5 g/dl: 
##STR3## 
(wherein R.sup.1 is a trivalent or tetravalent carbocyclic aromatic group 
or heterocyclic group, R.sup.2 is an aliphatic group having at least two 
carbon atoms, an alicyclic group, an aromatic aliphatic group, a 
carbocyclic aromatic group, a heterocyclic group or a polysiloxane group, 
R.sup.3 is a divalent organic group, R.sup.4 is 
##STR4## 
a hydrogen atom or a monovalent organic group, R.sup.5 is a hydrogen atom 
or a monovalent organic group, m is independently 1 or 2, n is 
independently 0 or 1, and m and n meet the relationship 
1.ltoreq.m+n.ltoreq.2). 
The second aspect of the present invention is directed to a method for 
preparing a photosensitive polymer which comprises the step of reacting a 
compound having a repeating unit represented by the formula (II) with a 
compound having a repeating unit represented by the formula (III) or a 
poly(amide)isoimide containing both the groups with a hydroxyphenyl 
group-containing amine represented by the formula (IV) at a temperature of 
from 0.degree. to 100.degree. C.: 
##STR5## 
(wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, m and n are as 
defined above). 
The third aspect of the present invention is directed to a photosensitive 
polymer composition comprising the following components (a), (b), (c) and 
(d) and a solvent: 
(a) a photosensitive polymer described in the above-mentioned first aspect, 
(b) a photopolymerization initiator or a sensitizer in an amount of from 0 
to 20% by weight based on the weight of the above-mentioned photosensitive 
polymer, 
(c) a azide compound in an amount of from 0.1 to 50% by weight based on the 
weight of the above-mentioned photosensitive polymer, and 
(d) a compound having a carbon-carbon double bond in an amount of from 0 to 
10% by weight based on the weight of the above-mentioned photosensitive 
polymer. 
The fourth aspect of the present invention is directed to a method for 
forming a patterned poly(amide)imide film which comprises the steps of 
coating a substrate with the above-mentioned photosensitive polymer 
composition, prebaking the composition at a temperature of from 30.degree. 
to 150.degree. C., irradiating it with an actinic radiation through a 
mask, developing, drying, and postbaking it at a temperature of from 
200.degree. to 500.degree. C. 
The photosensitive polymer of the present invention having the repeating 
unit represented by the formula (I) is a photosensitive polyamide-imide 
precursor in which m=1 and n=0, and a photosensitive polyimide precursor 
both in the case of m=n=1 and in the case of m=2 and n=0.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
A method for preparing a photosensitive polymer of the present invention 
will be described in detail. 
A poly(amide)isoimide can be easily prepared by further reacting, in 
accordance with a method described on page 631 of Proceedings of Second 
International Conference on Polyimides (1985), a reaction product of a 
tetracarboxylic dianhydride, a tricarboxylic anhydride (inclusive of its 
derivative, and the same shall apply hereinafter) or a reaction product of 
both of them with a diamine. 
The above-mentioned tetracarboxylic dianhydride, tricarboxylic anhydride 
and diamine can be represented by the formulae (V), (V') and (VI), 
respectively, and they will be described in detail. 
##STR6## 
(wherein R.sup.1 and R.sup.2 are as defined above, and Y is OH or Cl). 
When R.sup.1 is a carbocyclic aromatic group, this group preferably has at 
least one six-membered ring. In particular, R.sup.1 is a monocyclic 
aromatic group, a condensed polycyclic aromatic group, or a polycyclic 
aromatic group having several condensed rings or non-condensed rings 
(these rings are linked with each other directly or via a crosslinking 
group). 
Suitable examples of the above-mentioned crosslinking group are as follows: 
##STR7## 
In a certain case, Q.sup.1 in the above formulae is an alkyl group or an 
alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, 
which may be substituted by one or more of halogen atoms (preferably 
fluorine atoms), a cycloalkyl group, an aryl group or an allylene group, 
Q.sup.2 is a hydrogen atom, a cycloalkyl group, an aryl group, or in a 
certain case, an alkyl group having 1 to 4 carbon atoms and substituted by 
one or more of halogen atoms. 
Q.sup.1 and Q.sup.2 may be linked with each other via two crosslinking 
groups such as two --SO.sub.2 -- groups. 
In case that R.sup.1 is a heterocyclic group, a specific example of such a 
heterocyclic group is a five-membered or six-membered heterocyclic 
aromatic group containing oxygen, nitrogen and/or sulfur or a condensed 
ring of the same and a benzene nucleus. 
The carbocyclic aromatic group or the heterocyclic group represented by 
R.sup.1 may be substituted by one or more of, for example, a nitro group, 
an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a 
halogen atom (particularly a fluorine atom), a silyl group or a sulfamoyl 
group. 
The group represented by R.sup.1 may be either unsubstituted or substituted 
by, for example, a halogen atom (e.g., fluorine, chlorine or bromine), or 
one or more alkyl groups or alkoxy group having 1 to 4 carbon atoms. 
When R.sup.2 is the carbocyclic aromatic group, an example of a preferred 
group is a monocyclic aromatic group, a condensed polycyclic aromatic 
group or a non-condensed bicyciic aromatic group. When of this group is a 
non-condensed bicyclic group, the aromatic rings are linked with each 
other via a crosslinking group. In this case, the usable crosslinking 
group is the same as mentioned in the paragraph regarding R.sup.1. 
When R.sup.2 is the heterocyclic group, a particular example is a 
five-membered or six-membered heterocyclic aromatic group containing O,N 
and/or S. 
When R.sup.2 is the aliphatic group, a particular example is an alkylene 
group having 2 to 12 carbon atoms or another alkylene group in which an 
alkylene chain contains a hetero-atom, for example, an O, S or N atom. 
When R.sup.2 is the alicyclic group, an example is a cyclohexyl group or a 
dicyclohexylmethane group, and when R.sup.2 is an aromatic aliphatic 
group, a particular example is 1,3-, 1,4- or 2,4-bis-alkylenebenzene 
group, 4,4'-bis-alkylene-diphenyl group, 4,4'-bis-alkylenediphenyl ether 
group or the like. 
It is preferred that each of many R.sup.1 s present in a polymer is 
independently a non-substituted monocyclic aromatic group, a 
non-substituted condensed polycyclic aromatic group or a non-substituted 
non-condensed bicyclic aromatic group. In the last group, the aromatic 
rings are linked with each other via a crosslinking group such as --O-- or 
--CO--. 
On the other hand, each of R.sup.2 s is independently, in a certain case, a 
monocyclic aromatic group or a non-condensed bicyclic aromatic group 
having one or more of halogen atoms or alkyl groups or alkoxy groups 
having 1 to 4 carbon atoms as substituents, or it is preferably a 
non-substituted monocyclic aromatic aliphatic group or a non-substituted 
aliphatic group having 2 to 10 carbon atoms. 
When R.sup.2 is a polysiloxane group, this polysiloxane group is 
represented by the formula (VII) 
##STR8## 
wherein R.sup.6 is independently 
##STR9## 
(s is an integer of from 1 to 4), R.sup.7 is independently an alkyl group 
having 1 to 6 carbon atoms, a phenyl group or an alkyl-substituted phenyl 
group having 7 to 12 carbon atoms, and l is a value of 
1.ltoreq.l.ltoreq.100. 
Examples of the tetracarboxylic dianhydride represented by the formula (V) 
are as follows: 
Pyromellitic dianhydride, 
3,3',4,4'-benzophenone-tetracarboxylic dianhydride, 
2,3,3',4'-benzophenone-tetracarboxylic dianhydride, 
2,2',3,3'-benzophenone-tetracarboxylic dianhydride, 
3,3',4,4'-diphenyl-tetracarboxylic dianhydride, 
2,2',3,3'-diphenyl-tetracarboxylic dianhydride, 
bis(2,3-dicarboxyphenyl)-methane dianhydride, 
bis(3,4-dicarboxyphenyl)-methane dianhydride, 
2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride, 
bis(3,4-dicarboxyphenyl) ether dianhydride, 
bis(3,4-dicarboxyphenyl)-sulfone dianhydride, 
N,N-(3,4-dicarboxyphenyl)-N-methylamine dianhydride, 
3,3',4,4'-tetracarboxybenzoyloxy benzene dianhydride, 
2,3,6,7-naphthalene-tetracarboxylic dianhydride, 
1,2,3,5,6-naphthalene-tetracarboxylic dianhydride, 
thiophene-2,3,4,5-tetracarboxylic dianhydride, 
pyrazine-2,3,5,6-tetracarboxylic dianhydride, 
pyridine-2,3,5,6-tetracarboxylic dianhydride, 
2,3,3',4'-biphenyltetracarboxylic dianhydride, 
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and the like. 
Particularly preferable examples of tricarboxylic anhydride represented by 
the above-mentioned formula (V') are trimellitic anhydride and trimellitic 
anhydride chloride. 
Examples of the diamines represented by the above-mentioned formula (VI) 
include known compounds. 
Particular examples of the carbocyclic aromatic diamines are as follows: 
o-, m- and p-phenylenediamine, diaminotoluenes (e.g., 2,4-diaminotoluene), 
1,4-diamino-2-methoxybenzene 2,5-diaminoxylenes, 
1,3-diamino-4-chlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 
1,4-diamino-2-bromobenzene, 1,3-diamino-4-isopropylbenzene, 
4,4'-diaminodiphenyl-2,2-propane, 4,4'-diaminodiphenylmethane, 
2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 
4,4'-diaminodiphenyl thioether, 4,4'-diaminodiphenylsulfone, 
3,3'-diaminodiphenylsulfone, phenyl 4,4'-diaminobenzoate, 
2,2'-diaminobenzophenone, 4,4-diaminobenzophenone, 4,4'-diaminobenzyl, 
4-(4'-aminophenylcarbamoyl)-aniline, bis(4-aminophenyl)-phosphine oxide, 
bis(4-aminophenyl)-methyl-phosphine oxide, 
bis(3-aminophenyl)-methylsulfine oxide, bis(4-aminophenyl)-phenylphosphine 
oxide, bis(4-aminophenyl)-cyclohexylphosphine oxide, 
N,N-bis(4-aminophenyl)-N-phenylamine, 
N,N-bis(4-aminophenyl)-N-methylamine, 4,4'-diaminodiphenylurea, 
1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 
diaminofluoranthene, bis(4-aminophenyl)-diethylsilane, 
bis(4-aminophenyl)-dimethylsilane, 
bis(4-aminophenyl)-tetramethyldisiloxane, 3,4'-diaminodiphenyl ether, 
benzidine, 2,2'-dimethylbenzidine, 
2,2-bis[4-(4-aminophenoxy)phenyl]propane, 
bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene and the 
like. 
Examples of the heterocyclic diamines are as follows: 
2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-s-triazine, 
2,7-diamino-dibenzofuran, 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 
2,5-diamino-1,3,4-thiaziazole, 2,4-diamino-6-phenyl-s-triazine and the 
like. 
Furthermore, examples of the aliphatic diamine are as follows: 
Dimethylenediamine, trimethylenediamine, tetramethylenediamine, 
hexamethylenediamine, heptamethylenediamine, octamethylenediamine, 
nonamethylenediamine, decamethylenediamine, 2,2-dimethylpropylenediamine, 
2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 
4,4-dimethylheptanethylenediamine, 3-methylheptamethylenediamine, 
3-methoxyheptamethylenediamine, 5-methylnonamethylenediamine, 
2,11-diaminododecane, 1,12-diaminooctadecane, 
1,2-bis(3-aminopropoxy)ethane, diamines represented by the formula H.sub.2 
N(CH.sub.2).sub.3 O(CH.sub.2).sub.2 O(CH.sub.2).sub.3 NH.sub.2 and the 
like. 
Furthermore, suitable exemplary compounds of the alicyclic diamine include 
1,4-diaminocyclohexane, 4,4'-diamino-dicyclohexylmethane and the like. 
Suitable examples of the aromatic-aliphatic diamine include 
1,4-bis(2-methyl-4-aminopentyl)-benzene, 
1,4-bis(1,1-dimethyl-5-aminopentyl)-benzene, 1,3-bis(aminomethyl)-benzene, 
1,4-bis(aminomethyl)-benzene and the like. 
Moreover, exemplary compounds of the diaminopoly siloxane are as follows: 
##STR10## 
Next, the hydroxyphenyl group-containing amine represented by the formula 
(IV) will be described. 
In the formula (IV), R.sup.3 preferably is a divalent organic group having 
1 to 10 carbon atoms, i.e., a residue such as an aliphatic group, an 
alicyclic group, an aromatic group or an aromatic aliphatic group. 
However, this kind of group may contain a polar group such as a hydroxyl 
group, a carboxyl group, an ether, an ester, a ketone or the like. R.sup.4 
is preferably 
##STR11## 
a hydrogen atom or an organic group having 1 to 10 carbon atoms such as an 
aliphatic group, an alicyclic group, an aromatic group or an aromatic 
aliphatic group. However, this kind of group may contain a polar group 
such as a hydroxyl group, a carboxyl group, an ether, an ester, a ketone 
or the like. R.sup.5 preferably is a hydrogen atom or an organic group 
having 1 to 10 carbon atoms such as an aliphatic group or an alkoxy group. 
However, this kind of group may contain a polar group such as a hydroxyl 
group, a carboxyl group, an ether, an ester, a ketone or the like. 
Examples of the compound represented by the formula (IV) include the 
following compounds: 
##STR12## 
Preferable solvents which can be used in preparing the photosensitive 
polymer of the present invention (hereinafter referred to as simply 
"reaction solvent" at times) are as follows: 
N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 
dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, 
hexamethylphosphoramide, methylformamide, N-acetyl-2-pyrrolidone, ethylene 
glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol 
monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol 
dimethyl ether, cyclopentanone, cyclohexanone, cresol, 
.gamma.-butyrolactone, N,N-diethylacetamide, N,N-diethylformamide, 
N,N-dimethylmethoxyacetamide, tetrahydrofuran, N-methyl- -caprolactam, 
tetrahydrothiophene dioxide (sulpholane) and the like. 
Furthermore, this reaction can be carried out in a mixed solvent which can 
be obtained mixing the above-mentioned organic solvents. The 
above-mentioned preferable organic solvent, when used, can be diluted with 
another aprotic (neutral) organic solvent such as an aromatic, an 
alicyclic or an aliphatic hydrocarbon or its chlorinated derivative (e.g., 
benzene, toluene, xylene, cyclohexane, pentane, hexane, petroleum ether or 
methylene chloride), or it can be diluted with dioxane. 
In the presence of the above-mentioned solvent, the poly(amide)amic acid 
can be synthesized from the above-mentioned acid anhydride and diamine by 
a known process. 
In this case, for the purpose of improving the adhesion to a substrate, an 
aminosilane represented by the following formula (VIII) can be introduced 
to the terminal of the polymer. 
EQU NH.sub.2 --R.sup.8 --SiR.sup.9.sub.3--k.sup.X.sub.k (VIII) 
wherein R.sup.8 is 
##STR13## 
(s is an integer of from 1 to 4), R.sup.9 is independently an alkyl group 
or a phenyl group having 1 to 6 carbon atoms or an alkyl-substituted 
phenyl group having 7 to 12 carbon atoms, X is independently a 
hydrolyzable alkoxy group, an acetoxy group or a halogen, and k is a value 
of 1.ltoreq.k.ltoreq.3]. 
Next, examples of the aminosilane represented by the formula (VIII) are as 
follows: 
Aminomethyl-di-n-propoxymethylsilane, 
(.beta.-aminoethyl)-di-n-propoxymethylsilane, 
(.beta.-aminoethyl)-diethoxyphenylsilane, 
(.beta.-aminoethyl)-tri-n-propoxysilane, 
(.beta.-aminoethyl)-dimethoxymethylsilane, 
(.gamma.-aminopropyl)-di-n-propoxymethylsilane, 
(.gamma.-aminopropyl)-di-n-butoxymethylsilane, 
(.gamma.-aminopropyl)-trimethoxysilane, 
(.gamma.-aminopropyl)-triethoxysilane, 
(.gamma.-aminopropyl)-di-n-pentoxyphenylsilane, 
(.gamma.-aminopropyl)methoxy-n-propoxymethylsilane, 
(.delta.-aminobutyl)-dimethoxymethylsilane, 
(3-aminophenyl)-di-n-propoxymethylsilane, 
(4-aminophenyl)-tri-n-propoxysilane, 
[.beta.-(4-aminophenyl)-ethyl]-diethoxymethylsilane, 
[.beta.-(3-aminophenyl)-ethyl]-di-n-propoxyphenylsilane, 
[.gamma.-(4-aminophenyl)-propyl]-di-n-propoxymethylsilane, 
[.gamma.-(4-aminophenoxy)-propyl]-di-n-propoxymethylsilane, 
[.gamma.-(3-aminophenoxy)-propyl]-di-n-butoxymethylsilane, 
(.gamma.-aminopropyl)-methyl-dimethoxysilane, 
(.gamma.-aminopropyl)-methyl-diethoxysilane, 
(.gamma.-aminopropyl)-ethyl-di-n-propoxysilane, 
4-aminophenyl-trimethoxysilane, 3-aminophenyl-trimethoxysilane, 
4-aminophenyl-methyl-dimethoxysilane, 
3-aminophenyl-di-methyl-methoxysilane, 4-aminophenyl-tri-ethoxysilane and 
the like. 
In addition to these compounds, a monofunctional acid anhydride or amine 
can be added to the reaction system for the purpose of controlling the 
molecular weight of the poly(amide)amic acid. Examples of this kind of 
monofunctional compound are as follows: 
Phthalic anhydride, maleic anhydride, aniline, monoallylamine and the like. 
The thus synthesized polyamic acid can be easily converted into a 
polyisoimide with tile aid of, for example, a dehydrating agent such as 
N,N'-dicyclohexylcarbodiimide, trifluoroacetic anhydride or the like in 
accordance with the above-mentioned Proceedings of the Second 
International Conference on Polyimides. In this case, an imido group is 
formed at times, depending upon reaction conditions. 
##STR14## 
Although the exemplary reaction with the polyamic acid by the use of the 
dehydrating agent of N,N'-dicyclohexylcarbodiimide is elucidated above, it 
is not always necessary that all of the amic acid is converted into the 
isoimide. However, when the ratio of the isoimide in the polymer 
decreases, the ratio of the hydroxyphenyl group-containing amine to be 
added also decreases, so that sensitivity deteriorates. For this reason, 
it is preferred that the conversion into the isoimide is achieved as much 
as possible. 
Next, the amine represented by the formula (IV) is added to this 
poly(amide)isoimide, and the reaction is then carried out in the presence 
of a reaction solvent. The amount of the amine to be added to the isoimide 
may be more or less than the equimolar amount, but it is preferably in the 
vicinity of the equimolar amount. A reaction temperature is in the range 
of from 0.degree. to 100.degree. C., preferably from about 10.degree. to 
about 30.degree. C. A reaction time is preferably in the range of from 0.2 
to 30 hours, more preferably from about 1 to about 10 hours. 
In this way, the photosensitive polymer of the present invention 
represented by the formula (I) can be obtained. The logarithmic viscosity 
number of this polymer is preferably in the range of from 0.1 to 5 dl/g 
from the viewpoint of film-forming properties. Here, the logarithmic 
viscosity number is .eta..sub.inh which can be defined by the formula 
##EQU1## 
(wherein .eta. is a value measured in a solvent at a temperature of 
30.degree..+-.0.01.degree. C. at a concentration of 0.5 g/dl by the use of 
a Ubbelohde's viscometer, .eta..sub.o is a value of the same solvent at 
the same temperature by the use of the same viscometer, and C is a 
concentration of 0.5 g/dl). As the solvent for determining the 
.eta..sub.inh, there can be used the reaction solvent. 
The photosensitive polymer of the present invention can be stored intactly 
in the state of a solution. However, this solution may be added to a large 
amount of a non-solvent and the precipitated polymer is collected by 
filtration and then dried to obtain a powdery or massy solid, and the 
polymer can be stored in the form of such a solid. 
The photosensitive polymer composition of the present invention can be 
composed of the above-mentioned (a), (b), (c) and (d) and a solvent. 
The photosensitive polymer described in the paragraph (a) contains the 
repeating unit represented by the formula (I), but it is not always 
necessary that this kind of repeating unit is present in a concentration 
of 100%. However, in practice, it is preferred that the above-mentioned 
repeating unit is present in a concentration of 30 mol % or more of all 
the repeating units. As repeating units other than the repeating unit 
represented by the formula (I), any one can be used without restriction, 
but the following repeating units are practically used singly or in 
combination. 
##STR15## 
The concentration of the photosensitive polymer in the photosensitive 
polymer composition is from 2 to 50% by weight, preferably from 10 to 30% 
by weight. 
Examples of the photopolymerization initiator or the sensitizer described 
in the paragraph (b) include the following compounds, and they can be used 
singly or in combination. 
Benzoin, benzoin ether, benzophenone, p,p'-dimethylbenzophenone, 
4,4'-bis(diethylaminobenzophenone), Michler's ketone, 2-nitrofluorene, 
5-nitroacenaphthene, 4-nitro-1-naphthylamine, anthrone, 1,9-benzanthrone, 
dibenzalacetone, anthraquinone, 2-methylanthraquinone, 1-nitropyrene, 
1,8-dinitropyrene, pyrene-1,6-quinone, cyanoacridine, benzoquinone, 
1,2-naphthoquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone and the 
like. 
The amount of the photopolymerization initiator or the sensitizer to be 
used is in the range of from 0 to 20% by weight, preferably from 0 to 10% 
by weight based on the weight of the photosensitive polymer. 
Examples of the azide compound described in tile above-mentioned paragraph 
(c) include the following compounds, and they can be used singly or in 
combination. 
2,6-di(p-azidobenzal)-4-methylcyclohexanone, 
2,6-di(p-azidobenzal)cyclohexanone, 4,4'-diazidochalcone, 
4,4'-diazidobenzalacetone, 4,4'-diazidostilbene, 4,4'-diazidobenzophenone, 
4,4'-diazidodiphenylmethane, 4,4'-diazidophenylamine and the like. 
The amount of the azide compound to be added is in the range of from 0.1 to 
50% by weight, preferably from 1 to 20% by weight based on the weight of 
the photosensitive polymer. 
Examples of the compound having the carbon-carbon double bond described in 
the above-mentioned paragraph (d) include the following compounds, and 
they can be used singly or in combination. 
Butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, 
benzyl acrylate, carbitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl 
methacrylate, lauryl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl 
methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 
glycidyl methacrylate, N-methylolacrylamide, N-diacetoneacrylamide, 
N,N'-methylenebisacrylamide, N-vinylpyrrolidone, ethylene glycol 
diacrylate, diethyleneglycol diacrylate, triethylene glycol diacrylate, 
butylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl 
glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol 
diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 
pentaerythritol diacrylate, pentaerythritol triacrylate, 
trimethylolpropane triacrylate, trimethylol propanetrimethacrylate and the 
like. 
The amount of the compound having the carbon-carbon double bond to be used 
is in the range of from 0 to 10% by weight, preferably from 0 to 5% by 
weight based on the weight of the photosensitive polymer. 
In addition, a crosslinking auxiliary can be used in an amount of 10% by 
weight or less based on the weight of the photosensitive polymer, and 
examples of the cross-linking auxiliary include known polyvalent thiols 
such as pentaerythritol tetra(3-mercaptopropionate), pentaerythritol 
tetra(mercapto acetate) or the like. Moreover, a secondary material such 
as a dye or a pigment can also be used. 
The photosensitive polymer composition can be obtained by dissolving the 
compounds described in the paragraphs (a), (b), (c) and (d) in the 
above-mentioned reaction solvent. 
Next, the method for forming the patterned poly(amide)imide film by the use 
of the polymer composition of the present invention will be described. The 
polymer composition of the present invention can be applied on a substrate 
such as a silicone wafer, a metal plate, a plastic plate or a glass plate 
in a known manner such as spin coat, dipping or spray printing. The 
coating film is prebaked at a temperature of from 30.degree. to 
150.degree. C. for a period of several minutes to several tens of minutes 
by a heating means such as an electric furnace or a hot plate to remove 
most of the solvent present in the coating film therefrom. This coating 
film is then irradiated with an actinic radiation through a negative mask. 
Examples of the actinic radiation include X-rays, electron beams, 
ultraviolet rays, far ultraviolet rays and visible rays, but above all, 
the ultraviolet rays and the far ultraviolet rays are particularly 
suitable. Next, the unexposed portions on the coating film are dissolved 
and removed with a developing solution to obtain a relief pattern. The 
developing solution can be selected from the above-mentioned reaction 
solvents but can also be used in the form of a mixed solution of the same 
and a lower alcohol such as methanol, ethanol or propanol. 
The relief pattern, if necessary, is rinsed in the above-mentioned 
non-solvent, and it is then dried at a temperature of 150.degree. C. or 
less with the intention of stabilizing the relief pattern. After the 
prebaking, the film is peeled from the substrate at a suitable point of 
time, and it can also be used as a single film. The relief pattern polymer 
which has been prepared through the development has the form of a 
precursor, and therefore this polymer is then heated at a temperature of 
from 200.degree. to 500.degree. C., preferably 300.degree. to 400.degree. 
C. for a period of several tens of minutes to several hours by the 
above-mentioned heating means, whereby the patterned poly(amide)imide film 
is formed. In this case, the chemical reaction proceeds as follows. The 
photosensitive component is volatilized by the thermal decomposition to 
form a poly(amide)imide. 
##STR16## 
(wherein Q is a crosslinked photosensitive component). 
As described above, the patterned heat resistant poly(amide)imide film can 
be obtained from the photosensitive polymer of the present invention. 
The photosensitive polymer of the present invention can be applied to 
electronic materials, particularly passivation films for semiconductors, 
printed circuits and the like. 
As discussed above, the novel photosensitive polymer of the present 
invention can be prepared easily by the preparation method of the present 
invention, and the photosensitive polymer composition which is a solution 
obtained by adding suitable amounts of specific additives to a specific 
solvent and dissolving them therein has a practically sufficient 
sensitivity and permits forming a good pattern. In addition, the 
photosensitive polymer composition of the present invention is excellent 
in shelf stability, so that the change of a film thickness with time is 
little. 
EXAMPLES 
The present invention will be described in more detail in reference to 
examples, but these examples do not intend to limit the present invention. 
EXAMPLE 1 
A 1-liter flask equipped with a stirrer, a dropping funnel, a thermometer, 
a condenser and a nitrogen replacer was fixed in a thermostatic chamber. 
500 g of dehydrated and purified N-methyl-2-pyrrolidone (hereinafter 
referred to simply as "NMP"), 25.49 g (0.127 mol) of 4,4'-diaminophenyl 
ether (hereinafter referred to simply as "DDE") and 1.04 g (0.0182 mol) of 
allylamine were then placed in the flask, and stirring was continued to 
dissolve them. Furthermore, 21.97 g (0.0682 mol) of 
3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to 
simply as "BTDA") and 14.87 g (0.0682 mol) of pyromellitic dianhydride 
(hereinafter referred to simply as "PMDA") were added, and reaction was 
then carried out at 20.degree.-30.degree. C. for 8 hours, thereby 
obtaining a polyamic acid in which allylamine was added to a terminal. 
Afterward, 56.28 g (0.273 mol) of N,N'-dicyclohexylcarbodiimide 
(hereinafter referred to simply as "DCC") was added, and the reaction was 
further carried out at this temperature for 10 hours, so that the white 
precipitate of N,N'-dicyclohexylurea was deposited and a polyisoimide 
solution was obtained. 29.77 g (0.273 mol) of p-aminophenol was added to 
this solution, and the reaction was carried out at 20.degree.-30.degree. 
C. for 5 hours. This solution was filtered to remove the white precipitate 
of N,N'-dicyclohexylurea, and then added dropwise to a large amount of 
ethanol to precipitate the photosensitive polymer of the present 
invention. This polymer was collected by filtration and then dried 
overnight under reduced pressure at 50.degree. C. to isolate this polymer. 
The logarithmic viscosity number of the thus obtained polymer of the 
present invention in NMP was 1.13 dl/g. The infrared absorption spectrum 
of the polymer is shown in FIG. 1. 
EXAMPLE 2 
In the same device as in Example 1, 40.40 g (0.0934 mol) of 
bis[4-(4-aminophenoxy)phenyl]sulfone and 2.56 g (0.0120 mol) of 
p-aminophenyltrimethoxysilane were poured into 500 g of 
N,N-dimethylacetamide (hereinafter referred to simply as "DMAc"), and 
stirring was continued for dissolution. Next, 16.12 g (0.0500 mol) of BTDA 
and 10.91 g (0.0500 mol) of PMDA were added to this solution, and reaction 
was carried out at 20.degree.-30.degree. C. for 8 hours, thereby obtaining 
a polyamic acid in which p-aminophenyltrimethoxysilane was added to a 
terminal. Afterward, 41.30 g (0.200 mol) of DCC was added to this 
solution, and the reaction was further carried out at this temperature for 
10 hours, so that the white precipitate of N,N'-dicyclohexylurea was 
deposited and a polyisoimide solution was obtained. 21.84 g (0.200 mol) of 
p-aminophenol was added to this solution, and the reaction was carried out 
at 20.degree.-30.degree. C. for 5 hours. This solution was filtered to 
remove the white precipitate of N,N'-dicyclohexylurea therefrom, and then 
added dropwise to a large amount of ethanol to precipitate the 
photosensitive polymer of the present invention. This polymer was 
collected by filtration and then dried overnight under reduced pressure at 
50.degree. C. to isolate this polymer. The logarithmic viscosity number of 
the thus obtained polymer in NMP was 1.53 dl/g. 
EXAMPLE 3 
In the same device as in Example 1, 36.46 g (0.177 mol) of DDE was poured 
into 500 g of DMAc, and stirring was continued for dissolution. Next, 
34.77 g (0.159 mol) of PMDA and 3.47 g (0.0354 mol) of maleic anhydride 
were added to this solution, and reaction was carried out at 
20.degree.-30.degree. C. for 6 hours, thereby obtaining a polyamic acid in 
which maleic anhydride was added to a terminal. Afterward, 32.89 g (0.159 
mol) of DCC was added to this solution, and the reaction was further 
carried out at this temperature for 10 hours, so that the white 
precipitate of N,N'-dicyclohexylurea was deposited and a polyisoimide 
solution was obtained. 17.40 g (0.159 mol) of p-aminophenol was added to 
this solution, and the reaction was carried out at 20.degree.-30.degree. 
C. for 5 hours. This solution was filtered to remove the white precipitate 
of N,N'-dicyclohexylurea therefrom, and then added dropwise to a large 
amount of ethanol to precipitate the photosensitive polymer of the present 
invention. This polymer was collected by filtration and then dried 
overnight under reduced pressure at 50.degree. C. to isolate this polymer. 
The logarithmic viscosity number of the thus-obtained polymer of the 
present invention in NMP was 0.58 dl/g. 
EXAMPLE 4 
In the same device as in Example 1, 38.39 g (0.131 mol) of 
1,4-bis(4-aminophenoxy)benzene was poured into 500 g of NMP, and stirring 
was continued for dissolution. Next, 30.16 g (0.138 mol) of PMDA was added 
to this solution, and reaction was carried out at 20.degree.-30.degree. C. 
for 5 hours. Furthermore, 0.79 g (0.0138 mol) of allylamine was added and 
the reaction was further carried out for 5 hours, thereby obtaining a 
polyamic acid in which allylamine was added to a terminal. Afterward, 
42.79 g (0.207 mol) of DCC was added to this solution, and the reaction 
was additionally carried out at this temperature for 10 hours, so that the 
white precipitate of N,N'-dicyclohexylurea was deposited and a 
polyisoimide solution was obtained. 22.63 g (0.207 mol) of p-aminophenol 
was added to this solution, and the reaction was carried out at 
20.degree.-30.degree. C. for 6 hours. This solution was filtered to remove 
the white precipitate of N,N'-dicyclohexylurea therefrom, and then added 
dropwise to a large amount of ethanol to precipitate the photosensitive 
polymer of the present invention. This polymer was collected by filtration 
and then dried overnight under reduced pressure at 50.degree. C. to 
isolate this polymer. The logarithmic viscosity number of the thus 
obtained polymer in NMP was 1.32 dl/g. 
EXAMPLE 5 
In the same device as in Example 1, 36.54 g (0.182 mol) of DDE was poured 
into 500 g of NMP, and stirring was continued for dissolution. Next, 35.02 
g (0.182 mol) of trimellitic anhydride was added to this solution, and 
reaction was carried out at 20.degree.-30.degree. C. for 5 hours. 
Furthermore, 75.31 g (0.365 mol) of DCC was added to the solution and the 
reaction was carried out for 40 hours, so that the conversion of amic acid 
into isoimide and the condensation of a terminal amino group and a 
carboxyl group were achieved simultaneously, thereby obtaining a 
polyamide-isoamide solution. Afterward, 19.92 g (0.182 mol) of 
p-aminophenol was added to this solution, and the reaction was further 
carried out at 20.degree.-30.degree. C. for 8 hours. This solution was 
filtered to remove the white precipitate of N,N'-dicyclohexylurea 
therefrom, and then added dropwise to a large amount of ethanol to 
precipitate the photosensitive polymer of the present invention. This 
polymer was collected by filtration and then dried overnight under reduced 
pressure at 50.degree. C. to isolate this polymer. The logarithmic 
viscosity number of the thus obtained polymer in NMP was 0.33 dl/g. 
EXAMPLE 6 
In the same device as in Example 1, 31.76 g (0.0774 mol) of 
2,2-bis[4-(4-aminophenoxy)phenyl]propane was poured into 500 g of DMAc, 
and stirring was continued for dissolution. Next, 34.62 g (0.0967 mol) of 
diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride was added to this 
solution, and reaction was carried out at 20.degree.-30.degree. C. for 5 
hours. Furthermore, 4.22 g (0.0387 mol) of p-aminophenol was added to the 
solution and the reaction was further carried out for 5 hours, thereby 
obtaining a polyamic acid in which p-aminophenol was added to a terminal. 
Afterward, 39.91 g (0.193 mol) of DCC was added to this solution, and the 
reaction was further carried out at 20.degree.-30.degree. C. for 10 hours 
to deposit the white precipitate of N,N'-dicyclohexylurea. This solution 
was filtered to remove this white precipitate therefrom, and then added 
dropwise to a large amount of acetone to precipitate a polyisoimide. This 
polymer was collected by filtration and then dried overnight under reduced 
pressure at 50.degree. C. to isolate this polymer. Afterward, 15.00 g of 
the thus obtained polyisoimide and 100 g of dehydrated and purified DMAC 
were placed in a 200-ml flask equipped with a stirrer, a dropping funnel, 
a thermometer, a condenser and a nitrogen replacer fixed in a thermostatic 
chamber, and stirring was continued to dissolve the polyisoimide therein. 
3.59 g (0.0329 mol) of p-aminophenol was added to this solution, and the 
reaction was carried out at 20.degree.-30.degree. C. for 5 hours. The 
solution was then added dropwise to a large amount of ethanol to 
precipitate the photosensitive polymer of the present invention. This 
polymer was collected by filtration and then dried overnight under reduced 
pressure at 50.degree. C. to isolate this polymer. The logarithmic 
viscosity number of the thus obtained polymer in NMP was 0.42 dl/g. 
EXAMPLE 7 
In the same device as in Example 1, 21.46 g (0.0496 mol) of 
bis[4-(4-aminophenoxy)phenyl]sulfone, 12.32 g (0.0496 mol) of 
1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 0.81 g (0.0142 
mol) of allylamine were poured into 500 g of DMAC, and stirring was 
continued for dissolution. Next, 34.26 g (0.106 mol) of BTDA was added to 
this solution, and reaction was carried out at 20.degree.-30.degree. C. 
for 8 hours, thereby obtaining a polyamic acid in which allylamine was 
added to a terminal. Afterward, 43.87 g (0.213 mol) of DCC was added to 
this solution, and the reaction was further carried out at this 
temperature for 8 hours to deposit the white precipitate of 
N,N'-dicyclohexylurea. This white precipitate was removed by filtration, 
and the resultant filtrate was then added dropwise to a large amount of 
acetone to precipitate a polyisoimide. This polymer was collected by 
filtration and then dried overnight under reduced pressure at 50.degree. 
C. to isolate this polyisoimide. 
Afterward, 15.00 g of the thus obtained polyisoimide and 100 g of 
dehydrated and purified DMAC were placed in a 200-ml flask equipped with a 
stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen 
replacer fixed in a thermostatic chamber, and stirring was continued to 
dissolve the polyisoimide therein. 3.94 g (0.0361 mol) of p-aminophenol 
was added to this solution, and the reaction was carried out at 
20.degree.-30.degree. C. for 6 hours. The solution was then added dropwise 
to a large amount of ethanol to precipitate the photosensitive polymer of 
the present invention. This polymer was collected by filtration and then 
dried overnight under reduced pressure at 50.degree. C. to isolate this 
polymer. The logarithmic viscosity number of the thus obtained polymer in 
NMP was 1.46 dl/g. 
EXAMPLE 8 
4.5 g of each of the photosensitive polymers of the present invention which 
had been synthesized in Examples 1 to 7 was dissolved in 25.5 g of NMP, 
and a azide compound, if necessary a photopolymerization initiator or a 
sensitizer and a compound having a carbon-carbon double bond and the like 
were suitably added to the resultant solution, thereby preparing the 
photosensitive polymer compositions of the present invention. 
A silicone wafer was spin-coated with each composition, and the latter was 
then prebaked at 70.degree. C. for 40 minutes to form a uniform film 
thereon. Next, this film was exposed to the light from an ultra-high 
pressure mercury vapor lamp (20 mW/cm.sup.2) for various irradiation 
times, and then immersed in a mixed solution of 4 parts by volume of NMP 
and 1 part by volume of ethyl alcohol to develop the film. This developed 
film was rinsed in ethyl alcohol and then dried, whereby a fresh relief 
pattern was obtained. Each exposure necessary to give 0.5 in terms of a 
value obtained by normalizing the thickness of the developed film by that 
of the undeveloped film is set forth in Table 1 as sensitivity. Each 
relief pattern was calcined at 200.degree. C. for 30 minutes and 
additionally at 400.degree. C. for 30 minutes in an electric furnace, and 
as a result, the pattern did not crumble. According to the infrared 
absorption spectra of the polymers, it was confirmed that every 
photosensitive polymer, after the calcination, was converted into the 
poly(amide)imide. The infrared absorption spectrum of the polymer in 
Example 8-11 (after the calcination) is shown in FIG. 2. 
Furthermore, in order to inspect the stability of these photosensitive 
polymers with time, the rotational viscosities* of the respective 
photosensitive polymer compositions were measured immediately after the 
preparation of these compositions and after they were allowed to stand at 
room temperature for 1 month. The photosensitive compositions of the 
examples and the detailed values of the measured results are set forth in 
Table 1. 
FNT The rotational viscosity was a viscosity measured at a temperature of 
25.degree. C. by the use of an E type viscometer (trade name VISCONIC EMD 
made by Tokyo Keiki Co., Ltd.). 
COMATIVE SYNTHESIS EXAMPLE 1 
The same device and the same procedure as in Example 1 were utilized, and a 
polyamic acid solution having a logarithmic viscosity number of 1.1 dl/g 
was synthesized from 100 g of NMP, 12.34 g (0.0383 mol) of BTDA and 7.66 g 
(0.0383 mol) of DDE. Afterward, 14.19,g (0.0766 mol) of dimethylaminoethyl 
methacrylate was mixed with this solution to obtain a photosensitive 
polymer solution. 30 g of this solution was sampled, and an additive shown 
in Table 1 was added thereto. Next, in the same manner as in the 
above-mentioned examples, a photosensitive test and the stability of the 
photosensitive polymers with time were measured. The results are shown in 
Table 1. 
TABLE 1 
__________________________________________________________________________ 
Comp. ExampleExample or 
PolymerPhotosensitive 
CompoundDiazido 
or SensitizerPolymerization Initiator 
Double BondCarbon-carbonCompound 
coating film)(thickness 
ofSensitivity 
##STR17## 
__________________________________________________________________________ 
Example 8-1 
Example 1 
A-1*.sup.1) 0.45 g 
2-nitrofluorene 0.18 g 
-- 45 mJ/cm.sup.2 (4.5.mu.) 
##STR18## 
Example 8-2 
Example 2 
A-1 0.45 g 
2-nitrofluorene 0.18 g 
-- 40 mJ/cm.sup.2 (4.9.mu.) 
##STR19## 
Example 8-3 
Example 3 
A-1 0.45 g 
1-nitropyrene 0.23 g 
M-1*.sup.3) 0.23 g 
185 mJ/cm.sup.2 (3.7.mu.) 
##STR20## 
Example 8-4 
Example 4 
A-1 0.45 g 
5-nitroacenaphthene 0.23 g 
M-2*.sup.4) 0.23 g 
95 mJ/cm.sup.2 (4.7.mu.) 
##STR21## 
Example 8-5 
Example 5 
A-1 0.45 g 
benzanthrone 0.23 g 
-- 105 mJ/cm.sup.2 (2.5.mu.) 
##STR22## 
Example 8-6 
Example 6 
A-2*.sup.2) 0.23 g 
-- -- 90 mJ/cm.sup.2 (3.0.mu.) 
##STR23## 
Example 8-7 
Example 7 
A-2 0.23 g 
Michler's ketone 0.45 g 
-- 60 mJ/cm.sup.2 (4.8.mu.) 
##STR24## 
Comparative Example 1 
Comparative Example 1 
-- Michler's ketone 0.45 g 
-- 4600 mJ/cm.sup.2 (4.2.mu.) 
##STR25## 
__________________________________________________________________________ 
*.sup.1) A-1: 2,6di(p-azidobenzal)-4-methylcyclohexanone 
*.sup.2) A-2: 2,6di(p-azidobenzal)cyclohexanone 
*.sup.3) M-1: Trimethylolpropane trimethacrylate 
*.sup.4) M-2: Pentaerythritol triacrylate