DESCRIPTION
[Title of the Invention]
CURED FILM AND POSITIVE PHOTOSENSITIVE RESIN COMPOSITION
TECHNICAL FIELD [0001]
The present invention relates to a cured film and a positive type photosensitive resin composition. More specifically, it relates to a cured film suitable for use as the insulation film in an organic electroluminescent (hereinafter abbreviated as EL) element and as the substrate planarizing film in a thin film transistor (hereinafter abbreviated as TFT) for driving a displaying device containing an organic EL element and also relates to a positive type photosensitivity resin composition for forming the cured film as well as applications and a production method for the cured film.
BACKGROUND ART
[0002]
Organic EL display devices are now attracting attention as components of next generation
flat panel displays. An organic EL display device is a self-luminous type display device
utilizing electroluminescence from an organic compound and able to display images with a
wide view angle, high-speed response, and high contrast. Having a potential of made thinner
and lighter, organic EL display devices have become a major focus of research and
development in recent years.
[0003]
Organic EL display devices, however, have the problem of being poor in long term reliability.
Organic luminescent materials are generally low in resistance to gas components and
moisture, and if exposed to them, they can suffer a decrease in light emission luminance or
shrinkage of pixels. Here, the term "shrinkage of pixels" means the phenomenon of a
decrease in light emission luminance or lighting failure at the edges of pixels. To provide a
display element with improved long term reliability, it is essential not only to develop an
organic luminescence material with increased durability, but also to develop peripheral
materials, such as planarizing layer covering the drive circuit and insulation layer covering
the first electrode, that have improved characteristics. If made of a photosensitive resin
composition, a planarizing layer and insulation layer as described above can be processed
easily into desired patters. In particular, the use of a positive type photosensitive resin
composition is preferred because of being suitable for alkali development with a high
resolution.
[0004]
Most positive type photosensitive resin compositions proposed so far are mixtures of an

alkali-soluble resin and an o-quinone diazide compound as photosensitive component, and they commonly use a polyimide precursor (see, for example, Patent document 1) or a polybenzoxazole precursor (see, for example, Patent document 2) as the resin.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
[0005]
[Patent document 1] Japanese Unexamined Patent Publication (Kokai) No. 2002-91343
[Patent document 2] Japanese Unexamined Patent Publication (Kokai) No. 2002-116715
SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0006]
The materials proposed in the above Patent documents, however, cannot be said to show
required performance in terms of long term reliability although they are preferred from the
viewpoint of being able to provide an insulation layer having a forward tapered cross section.
In view of the above problems, an object of the present invention is to provide a cured film
and a positive type photosensitive resin composition that ensures a long term reliability
without causing a decrease in light emission luminance or shrinkage of pixels.
MEANS OF SOLVING THE PROBLEMS
[0007]
The cured film according to the present invention is composed mainly of a cured product of a
photosensitive resin composition including an alkali-soluble resin (a), a photoacid generating
agent (b), at least one compound (c) selected from the group consisting of cyclic amides,
cyclic ureas, and derivatives thereof, and a thermal crosslinking agent (d), the thermal
crosslinking agent (d) containing an epoxy compound, oxetanyl compound, isocyanate
compound, acidic group-containing alkoxymethyl compound, and/or acidic group-containing
methylol compound, and the total content of the compound (c) in the cured film being 0.005
mass% or more and 5 mass% or less.
[0008]
The positive type photosensitive resin composition according to the present invention
includes an alkali-soluble resin (a), a photoacid generating agent (b), at least one compound
(c) selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof,
a thermal crosslinking agent (d), and an organic solvent (e), the thermal crosslinking agent
(d) containing an epoxy compound, oxetanyl compound, isocyanate compound, acidic
group-containing alkoxymethyl compound, and/or acidic group-containing methylol
compound, the compound (c) accounting for 0.1 part by mass or more and 15 parts by mass
or less relative to 100 parts by mass of the alkali-soluble resin (a), and the organic solvent

(e) accounting for 100 to 3,000 parts by mass relative thereto.
ADVANTAGEOUS EFFECT OF THE INVENTION
[0009]
The cured film and the positive type photosensitive resin composition according to the
present invention ensure a long term reliability without causing a decrease in light emission
luminance or shrinkage of pixels. The use of the cured film and the positive type
photosensitive resin composition make it possible to provide an organic EL display device
high in long term reliability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010]
[Fig. 1] Fig. 1(a) to (f) are schematic diagrams illustrating a typical method for producing a
substrate for an organic EL display device.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0011]
An embodiment of the present invention is described in detail below.
As a result of intensive studies, the present inventors have found that some acidic gases
generated in trace amounts from insulation layers are a factor in the decrease in long term
reliability of an organic EL device. More specifically, acidic gases, such as sulfur dioxide,
carbon dioxide, and hydrogen sulfide, generated from planarizing layers or insulation layers
are accumulated near the interface between an electrode and a luminescence layer to cause
the phenomenon called shrinkage of pixels, i.e., a decrease in light emission luminance or
lighting failure at the edges of pixels.
The present inventors found that this problem can be solved according to the two
embodiments described below.
[0012]
The first embodiment of the present invention provides a cured film that is composed mainly
of a cured product of a photosensitive resin composition including an alkali-soluble resin (a),
a photoacid generating agent (b), at least one compound (c) selected from the group
consisting of cyclic amides, cyclic ureas, and derivatives thereof, and a thermal crosslinking
agent (d), the thermal crosslinking agent (d) containing an epoxy compound, oxetanyl
compound, isocyanate compound, acidic group-containing alkoxymethyl compound, and/or
acidic group-containing methylol compound, and the total content of the compound (c) in the
cured film being 0.005 mass% or more and 5 mass% or less. When used in planarizing
layers or insulation layers, this serves to prevent a decrease in light emission luminance or
shrinkage of pixels and provide an organic EL device having high long-term reliability.
[0013]

The second embodiment of the present invention provides a positive type photosensitive
resin composition that includes an alkali-soluble resin (a), a photoacid generating agent (b),
at least one compound (c) selected from the group consisting of cyclic amides, cyclic ureas,
and derivatives thereof, a thermal crosslinking agent (d), and an organic solvent (e), the
thermal crosslinking agent (d) containing an epoxy compound, oxetanyl compound,
isocyanate compound, acidic group-containing alkoxymethyl compound, and/or acidic
group-containing methylol compound, the compound (c) accounting for 0.1 part by mass or
more and 15 parts by mass or less relative to 100 parts by mass of the alkali-soluble resin
(a), and the organic solvent (e) accounting for 100 to 3,000 parts by mass relative thereto.
When used in planarizing layers or insulation layers, this positive type photosensitive resin
composition serves to prevent a decrease in light emission luminance or shrinkage of pixels
and provide an organic EL device having high long-term reliability.
Here, the cured film according to the first embodiment can be produced by curing the
positive type photosensitive resin composition according to the second embodiment.
[0014]
First, the first embodiment is described in detail.
In the cured film according to the present invention, the total content of the at least one
compound (c) selected from the group consisting of cyclic amides, cyclic ureas, and
derivatives thereof is 0.005 mass% or more and 5 mass% or less. It is considered that if at
least one compound (c) selected from the group consisting of cyclic amides, cyclic ureas,
and derivatives thereof is contained, the compound (c) works as a quencher for acidic gases
to serve to prevent a decrease in light emission luminance or shrinkage of pixels and provide
an organic EL device having high long-term reliability.
[0015]
The content by mass% of the at least one compound (c) selected from the group consisting
of cyclic amides, cyclic ureas, and derivatives thereof in the cured film can be determined by
examining a specimen taken from the cured film by the purge-and-trap method, the TPD-MS
method, or the like to measure the mass of the compounds and analyzing the
measurements based on the specific gravity of the alkali-soluble resin (a) component to
calculate the content by mass% of the compound (c) in the cured film.
[0016]
The total content of the at least one compound (c) selected from the group consisting of
cyclic amides, cyclic ureas, and derivatives thereof in the cured film is preferably 0.005
mass% or more, more preferably 0.05 mass% or more, and preferably 5 mass% or less,
more preferably 3 mass% or less, relative to the total mass of the cured film. The quencher
effect can be invoked if it is 0.005 mass% or more, whereas the outgassing of the
compounds themselves, which can cause a decrease in reliability, can be prevented if it is 3
mass% or less.
[0017]

The photosensitive resin composition used in the cured film according to the present invention contains an alkali-soluble resin (a). For the present invention, alkali-solubility test is performed by dissolving a resin sample in y-butyrolactone to prepare a solution, spreading it over a silicon wafer, prebaking it at 120°C for 4 minutes to form a prebaked film with a film thickness of 10 urn ± 0.5 urn, immersing the prebaked film in an aqueous solution containing 2.38 parts by mass of tetramethyl ammonium hydroxide at 23±1°C for 1 minute, rinsing it with pure water, and determining the dissolution rate from the decrease in film thickness, and the resin is judged to be alkali-soluble if the rate is 50 nm/min or more. [0018]
Specific examples of the alkali-soluble resin (a) include, but not limited to, polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyaminoamide, polyamide, polymers obtainable from radical-polymerizable monomers having alkali-soluble groups, cardo resin, phenol resin, cyclic olefin polymers, and siloxane resin. Two or more of these resins may be contained together. Of these alkali-soluble resins, those with a high heat resistance and a smaller outgassing rate at high temperatures are preferred. Specifically, it is preferable to use one or more alkali-soluble resins selected from the group consisting of polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, and copolymers thereof. [0019]
Alkali-soluble resins selected from the group consisting of polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, and copolymers thereof that can serve as the alkali-soluble resin (a) preferably has an acidic group such as, for example, carboxyl group, phenolic hydroxyl group, and sulfonic acid group in the structural unit of the resin and/or at the chain end of the backbone thereof to develop such alkali-solubility as described above. In addition, it is preferable to contain fluorine atoms, because they work to develop water repellency at the interface between the film and the base material in the development step that uses the aqueous alkali solution to prevent the infiltration of the aqueous alkali solution to the interface. The content of the fluorine atoms is preferably 5 parts by mass or more relative to 100 parts by mass of the alkali-soluble resin from the viewpoint of effective prevention of the infiltration of the aqueous alkali solution to the interface, whereas it is preferably 20 parts by mass or less relative thereto from the viewpoint of its solubility in the aqueous alkali solution. [0020]
A polyimide compound as described above has a structural unit as represented by general formula (2) given below, whereas a polyimide precursor and a polybenzoxazole precursor have a structural unit as represented by general formula (3) given below. Two or more of these alkali-soluble resins may be contained, and a copolymer resin of a structural unit as represented by general formula (2) and a structural unit as represented by general formula (3) may be used.


In general formula (2), R3 is a tetravalent to decavalent organic group, and R4 is a divalent to octavalent organic group. R5 and R6 are each a carboxyl group or a phenolic hydroxyl group and may be identical to or different from each other. Furthermore, p and q are each an integer of 0 to 6. [0022]

In general formula (3), R7 is a divalent to octavalent organic group, and R8 is a divalent to
octavalent organic group. R9 and R10 each denote a phenolic hydroxyl group or COOR11 and
may be identical to or different from each other. R11 denotes a hydrogen atom or a
monovalent hydrocarbon group containing 1 to 20 carbon atoms. Furthermore, r and s are
each an integer of 0 to 6. Here, the relation of r + s > 0 holds.
[0023]
The alkali-soluble resin, which is selected from the group consisting of polyimide, polyimide
precursors, polybenzoxazole, polybenzoxazole precursors, and copolymers thereof,
preferably contains 5 to 100,000 structural units that are represented by general formula (2)
or (3). It may contain another structural unit in addition to the structural units that are
represented by general formula (2) or (3). In this case, it is preferable for the structural units
that are represented by general formula (2) or (3) to account for 50 mol% or more of the total
number of structural units.
[0024]
In general formula (2) given above, R3-(R4)P represents an acid dianhydride residue. R3 is a
tetravalent to decavalent organic group and in particular, it is preferably an organic group
containing 5 to 40 carbon atoms and having an aromatic ring or a cyclic aliphatic group.
[0025]
Specific examples of the acid dianhydride include pyromellitic acid dianhydride,

3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 2,3,3',4'-biphenyl tetracarboxylic acid
dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone
tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride,
2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) propane
dianhydride, 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)
ethane dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride,
bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyI) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy) phenyl} fluorene acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, and 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, as well as aromatic tetracarboxylic acid dianhydrides such as those dianhydrides having structures as shown below and aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride and 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride. Two or more of these may be used in combination. [0026]

(R12 denotes an oxygen atom, C(CF3)2, or C(CH3)2. R13 and R14 are each a hydrogen atom
or a hydroxyl group.
[0027]
In general formula (3) given above, R7-(R9)r represents an acid residue. R7 is a divalent to
octavalent organic group and in particular, it is preferably an organic group containing 5 to 40
carbon atoms and having an aromatic ring or a cyclic aliphatic group.
[0028]
Examples of the acid components include dicarboxylic acids such as terephthalic acid,
isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl) hexafluoropropane,
biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid;
tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and
biphenyl tricarboxylic acid; and tetracarboxylic acids including aromatic tetracarboxylic acids

such as pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl
tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone
tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid,
2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)
hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl) ethane, 1,1-bis(2,3-dicarboxyphenyl) ethane, bis(3,4-dicarboxyphenyl) methane, bis(2,3-dicarboxyphenyl) methane, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalene tetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, and others having structures as shown below, and aliphatic tetracarboxylic acids such as butane tetracarboxylic acid and 1,2,3,4-cyclopentane tetracarboxylic acid. Two or more of these may be used in combination. T00291

(R12 denotes an oxygen atom, C(CF3)2, or C(CH3)2. R13 and R14 are each a hydrogen atom
or a hydroxyl group.
[0030]
In tricarboxylic acids and tetracarboxylic acids, in particular, one or two carboxyl groups
correspond to the R9 group in general formula (3). In the dicarboxylic acids, tricarboxylic
acids, and tetracarboxylic acids given above, it is preferable for one to four hydrogen atoms
to be substituted by R9 groups as represented by general formula (3), more preferably
substituted by hydroxyl groups. These acids may be used in their original form or in the form
of an anhydride or an active ester.
[0031]
R4-(R6)q in general formula (2) given above and R8-(R10)S in general formula (3) given above
each represent a diamine residue. R4 and R10 are each a divalent to octavalent organic
group and in particular, it is preferably an organic group containing 5 to 40 carbon atoms and
having an aromatic ring or a cycloaliphatic group.
[0032]
Specific examples of the diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl
ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane,

1,4-bis(4-aminophenoxy) benzene, benzidine, m-phenylene diamine, p-phenylene diamine,
1,5-naphthaIene diamine, 2,6-naphthalene diamine, bis(4-aminophenoxy) biphenyl,
bis{4-(4-aminophenoxy) phenyl} ether, 1,4-bis(4-aminophenoxy) benzene,
2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyI, 3,3'-diethyl-4,4'-diaminobiphenyl,
2,2',3,3,-tetramethyl-4,4'-diaminobiphenyl, S.S'^^'-tetramethyM^'-diaminobiphenyl,
2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, and 9,9-bis(4-aminophenyl) fluorine; compounds listed above in which at least part of the hydrogen atoms in the aromatic rings are substituted by alkyl groups or halogen atoms; aliphatic cyclohexyl diamines and methylene biscyclohexyl amines; and diamines having structures as given below. Two or more of these may be used in combination. [0033]

R12 denotes an oxygen atom, C(CF3)2, or C(Chb)2. R13 to R16 are each a hydrogen atom or a
hydroxy! group.
[0034]

These diamines may be used in the form of the original diamines or in the form of
corresponding diisocyanate compounds or trimethylsilylated diamines.
[0035]
The chain ends of these alkali-soluble resins may be capped by a monoamine having an
acidic group, acid anhydride, acid chloride, or monocarboxylic acid to form alkali-soluble
resins having acidic groups at backbone chain ends.
[0036]
Preferable examples of these monoamines include 5-amino-8-hydroxyquinoline,
1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene,
1 -hydroxy-5-aminonaphthalene, 1 -hydroxy-4-aminonaphthalene,
2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene,
2-hydroxy-5-aminonaphthalene, 1 -carboxy-7-aminonaphthalene,
1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthaIene,
2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene,
2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid,
4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosaiicylic acid, 6-aminosalicylic acid,
3-amino-4,6-dihydroxy pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol,
2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may
be used in combination.
[0037]
Preferable examples of these acid anhydrides, acid chlorides, and monocarboxylic acids
include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride,
cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride; monocarboxylic acids
such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol,
1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene,
1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene,
1-mercapto-6-carboxynaphthalene, and 1-mercapto-5-carboxynaphthalene; those monoacid
chloride compounds that can be produced therefrom by converting their carboxyl groups into
acid chloride groups; those monoacid chloride compounds that can be produced from
dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid,
cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene,
1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene by converting only one of their
carboxyl groups into an acid chloride group; and active ester compounds that can be
produced by reacting a monoacid chloride compound with N-hydroxybenzotriazole or
N-hydroxy-5-norbornene-2,3-dicarboxyimide. Two or more of these may be used in
combination.
[0038]
The aforementioned end capping agents such as monoamine, acid anhydride, acid chloride,
and monocarboxylic acid preferably account for 2 to 25 mol% of the total quantity, which

accounts for 100 mol%, of the acids and amine components present in the alkali-soluble
resin.
[0039]
End capping agents introduced in an alkali-soluble resin can be detected easily by methods
as described below. For example, a resin specimen containing an end capping agent is
dissolved in an acidic solution to decompose it into amine components and acid components,
that is, constituent units of the resin, and then the end capping agent can be detected easily
by gas chromatography (GC) or NMR spectroscopy. In another method, detection can be
carried out by subjecting a resin specimen containing an end capping agent directly to
pyrolysis gas chromatograph (PGC), infrared spectroscopy, or 13C-NMR spectroscopy.
[0040]
The alkali-soluble resin (a) is synthesized by a generally known method. In the case where
the alkali-soluble resin is a polyamic acid and polyamic acid ester, good production methods
include, for example, a method in which a tetracarboxylic acid dianhydride and a diamine
compound are reacted at a low temperature, a method in which a diester is obtained from a
tetracarboxylic acid dianhydride and an alcohol, followed by its reaction with an amine in the
presence of a condensation agent, a method in which a diester is obtained from a
tetracarboxylic acid dianhydride and an alcohol, followed by conversion of the remaining
dicarboxylic acid into an acid chloride and its reaction with an amine.
[0041]
In the case where the alkali-soluble resin is polyhydroxyamide which is a polybenzoxazole
precursor, its production can be achieved by subjecting a bisaminophenol compound and a
dicarboxylic acid to condensation reaction. More specifically, good production methods
include a method in which a dehydration-condensation agent such as dicyclohexyl
carbodiimide (DCC) and an acid are reacted, followed by adding a bisaminophenol
compound and a method in which a tertiary amine such as pyridine is added to a solution of
a bisaminophenol compound, followed by dropping it to a solution of a dicarboxylic acid
dichloride.
[0042]
In the case where the alkali-soluble resin is a polyimide, it can be produced by, for example,
heating a polyamic acid or polyamic acid ester as prepared by the aforementioned method
or subjecting them to chemical treatment with an acid or a salt group to cause dehydration
cyclization.
[0043]
In the case where the alkali-soluble resin is a polybenzoxazole, it can be produced by, for
example, heating a polybenzoxazole precursor (polyhydroxyamide) as prepared by the
aforementioned method or subjecting it to chemical treatment with an acid or a salt group to
cause dehydration cyclization.
[0044]

To produce a polymer including radical-polymerizable monomers with alkali-soluble groups that can be used as the alkali-soluble resin (a), radical-polymerizable monomers with phenolic hydroxy! groups or carboxyl groups are used to develop alkali-solubility. Such radical-polymerizable monomers with phenolic hydroxyl groups or carboxyl groups include , for example, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, which may be substituted by an alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester, or carboxy group; polyhydroxyvinyl phenols such as vinyl hydroquinone, 5-vinyl pyrogallol, 6-vinyl pyrogallol, and 1-vinyl fluoroglycinol; o-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid, which may be substituted by an alkyl, alkoxy, halogen, nitro, cyano, amide, or ester group; methacrylic acid and acrylic acid, which may be substituted by an a-haloalkyl, alkoxy, halogen, nitro, or cyano group; divalent unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid, and 1,4-cyclohexene dicarboxylic acid, as well as methyl, ethyl, propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, phenyl, and o-, m-, p-toluyl half esters and half amides thereof. [0045]
Of these, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, which may be substituted by alkyl or alkoxy, have been preferred from the viewpoint of the sensitivity and resolution in the patterning step, proportion of the remaining film after the development step, heat-resistant deformability, solvent resistance, adhesion with the substrate, storage stability of the solution, etc. These monomers may be used singly or as a mixture of two or more thereof. [0046]
To produce a polymer including radical-polymerizable monomers with phenolic hydroxyl
groups or carboxyl groups that can be used as the alkali-soluble resin (a), other
radical-polymerizable monomers may be used. Useful examples of such other
radical-polymerizable monomers include styrene, which may be substituted at the a-, o-, m-,
or p-position by an alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, or ester group;
diolefins such as butadiene, isoprene, and chloroprene; methacrylic acids and acrylic acids
esterified with methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, pentyl, neopentyl,
isoamylhexyl, cyclohexyl, adamanthyl, allyl, propargyl, phenyl, naphthyl, anthracenyl,
anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenethyl, cresyl, glycidyl,
1,1,1-trifluoroethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, triphenylmethyl,
tricyclo[5.2.1.02'6]decane-8-yl (commonly called dicyclopentenyl), cumyl,
3-(N,N-dimethylamino)propyl, 3-(N,N-dimethylamino)ethyl, furyl, or furfuryl; anilides and amides of methacrylic acid or acrylic acid; and N,N-dimethyl, N,N-diethyl, N,N-dipropyl, N,N-diisopropyl, anthranilamide, acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, N-phenyl maleinimide, N-(4-hydroxyphenyl) maleinimide, N-methacryloyl phthalimide, and N-acryloyl phthalimide. These may be used singly or as a mixture of two or

more thereof. [0047]
Of these, styrene, which may be substituted by alkyl, alkoxy, halogen, or haloalkyl at the a-, o-, m-, or p-position; butadiene and isoprene; and esterification products of methacrylic acid or acrylic acid with methyl, ethyl, n-propyl, n-butyl, glycidyl, ortricycleo[5.2.1.02,6]decane-8-yl are particularly preferred from the viewpoint of the sensitivity and resolution in the patterning step, proportion of the remaining film after the development step, heat-resistant deformability, solvent resistance, adhesion with the substrate, storage stability of the solution, etc. When a copolymer of a radical-polymerizable monomer having a phenolic hydroxyl group and other radical-polymerizable monomer is used as the alkali-soluble resin, the other radical-polymerizable monomer preferably accounts for 40 parts by mass or less, particularly preferably 5 to 30 parts by mass, relative to the total quantity, which accounts for 100 parts by mass, of the radical-polymerizable monomer having a phenolic hydroxyl group and the other radical-polymerizable monomer. When a copolymer of a radical-polymerizable monomer having a carboxyl group and other radical-polymerizable monomer is used as the alkali-soluble resin, the other radical-polymerizable monomer preferably accounts for 90 parts by mass or less, particularly preferably 10 to 80 parts by mass, relative to the total quantity, which accounts for 100 parts by mass, of the radical-polymerizable monomer having a carboxyl group and the other radical-polymerizable monomer. Alkali development may be difficult to achieve if the proportion of these other radical-polymerizable monomers is larger than the aforementioned values specified for the radical-polymerizable monomers with phenolic hydroxyl groups or carboxyl groups. [0048]
Solvents useful for production of a polymer containing radical-polymerizable monomers with alkali-soluble groups include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; and esters such as methyl acetate, ethyl acetate, propyl

acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methyl propionate, hydroxymethyl acetate, hydroxyethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutannoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate. It is preferable for these solvents to account for 20 to 1,000 parts by mass relative to 100 parts by mass of the radical-polymerizable monomers. [0049]
Useful polymerization initiators for the production of a polymer containing a radical-polymerizable monomer with an alkali-soluble group include, for example, azo compounds such as 2,2'-azo-bis-isobutyronitrile, 2,2'-azo-bis-(2,4-dimethyl valeronitrile), and 2,2'-azo-bis-(4-methoxy-2,4-dimethyl valeronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, and 1,1'-bis-(t-butyl peroxy) cyclohexane; and hydrogen peroxide. When adopting a peroxide as radical polymerization initiator, the peroxide may be used with a reduction agent to work as a redox type initiator. [0050]
Such a polymer containing a radical-polymerizable monomer with an alkali-soluble group preferably has a polystyrene based weight average molecular weight of 2,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 5,000 to 30,000, as determined by gel permeation chromatography. Developability and sensitivity tend to deteriorate when the weight average molecular weight is more than 100,000, whereas the pattern shape, resolution, developability, and heat resistance tend to deteriorate when it is less than 2,000. [0051]
These polymers containing a radical-polymerizable monomer with an alkali-soluble group may be used singly or as a combination of two or more thereof. Another good alkali-soluble resin synthesis method is to introduce a protective group in the carboxyl group or phenolic

hydroxy! group before polymerization and remove the protective group after polymerization
to develop alkali-solubility. In addition, the transparency to visible light and the softening
point may be controlled by hydrogenation etc.
[0052]
A cardo resin can serve as the alkali-soluble resin (a) if its backbone has a cardo structure
characterized by a cyclic structure having a quaternary carbon atom to which two other
cyclic structures are bonded. Atypical cardo structure is a combination of a fluorene ring and
benzene rings bonded thereto.
[0053]
Specific examples of such a backbone structure characterized by a cyclic structure having a
quaternary carbon atom to which two other cyclic structures are bonded include fluorene
backbone, bisphenol fluorene backbone, bisaminophenyl fluorene backbone, fluorene
backbone having an epoxy group, and fluorene backbone having an acrylic group.
[0054]
A cardo resin can be produced by polymerization of cardo structure-based backbones
caused by reaction between functional groups bonded the backbones. A cardo resin has a
structure (cardo structure) characterized by a backbone chain and bulky side chains each
bonded thereto through one atom to form a cyclic structure extended nearly perpendicular to
the backbone chain.
[0055]
Specific examples of monomers having a cardo structure include cardo structure-containing
bisphenols such as bis(glycidyloxyphenyl) fluorene type epoxy resin,
9,9-bis(4-hydroxyphenyl) fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl) fluorene;
9,9-bis(cyanoalkyl) fluorenes such as 9,9-bis(cyanomethyl) fluorene; and 9,9-bis(aminoalkyl)
fluorenes such as 9,9-bis(3-aminopropyl) fluorene.
[0056]
The cardo resin is typically a polymer produced through polymerization of a monomer having
a cardo structure, but it may be a copolymer with other copolymerizable monomers.
[0057]
Generally known methods such as ring opening polymerization and addition polymerization
can be used for the polymerization of the monomers described above.
[0058]
Phenol resins useful as the alkali-soluble resin (a) include novolac phenol resins and resol
phenol resins, which can be produced by subjecting a phenol or a mixture of a plurality of
different phenols, selected from various available ones, to condensation polymerization with
an aldehyde such as formalin.
[0059]
The phenols that can serve for producing novolac phenol resins or resol phenol resins
include, for example, phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethyl phenol, 2,4-dimethyl

phenol, 2,5-dimethyl phenol, 2,6-dimethyl phenol, 3,4-dimethyl phenol, 3,5-dimethyl phenol,
2,3,4-trimethyl phenol, 2,3,5-trimethyI phenol, 3,4,5-trimethyl phenol, 2,4,5-trimethyl phenol,
methylene bisphenol, methylene bis-p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl
resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxy
phenol, p-methoxy phenol, p-butoxy phenol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol,
2,3-diethyl phenol, 2,5-diethyl phenol, p-isopropyl phenol, a-naphthol, and 8-naphthol, which
may be used singly or as a mixture of two or more thereof.
[0060]
Useful aldehydes include, in addition to formalin, para-formaldehyde, acetoaldehyde,
benzaldehyde, hydroxybenzaldehyde, and chloroacetoaldehyde, which may be used singly
or as a mixture of two or more thereof.
[0061]
It is preferable for a phenol resin used as the alkali-soluble resin (a) to have a
polystyrene-based weight average molecular weight in the range of 2,000 to 50,000, more
preferably in the range of 3,000 to 30,000, as determined by gel permeation chromatography.
Developability and sensitivity tend to deteriorate when the weight average molecular weight
is more than 50,000, whereas the pattern shape, resolution, developability, and heat
resistance tend to deteriorate when it is less than 2,000.
[0062]
Cyclic olefin polymers useful as the alkali-soluble resin (a) include homopolymers or
copolymers of a cyclic olefin monomer having a cyclic structure (alicyclic or aromatic ring)
and a carbon-carbon double bond. Such a cyclic olefin polymer may also contain a monomer
that is not a cyclic olefin monomer.
[0063]
Monomers useful to produce such a cyclic olefin polymer include cyclic olefin monomers
having protonic polar groups, cyclic olefin monomers having non-protonic polar groups,
cyclic olefin monomers having no polar groups, and non-cyclic-olefin monomers. Here, such
non-cyclic-olefin monomers may have protonic polar groups or other polar groups or may be
free of polar groups.
[0064]
Specific examples of the cyclic olefin monomers having protonic polar groups include cyclic
olefins containing carboxyl groups such as 5-hydroxycarbonyl bicyclo[2.2.1]hept-2-ene,
5-methyl-5-hydroxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-carboxymethyl-5-hydroxycarbonyl
bicyclo[2.2.1 ]hept-2-ene, 5-exo-6-endo-dihydroxycarbonyl bicyclo[2.2.1 ]hept-2-ene,
8-hydroxycarbonyl tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-methyl-8-hydroxycarbonyl
tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, and 8-exo-9-endo-dihydroxycarbonyl
tetracyclo[4.4.0.12-5.17'10]dodeca-3-ene; and cyclic olefins containing hydroxyl groups such
as 5-(4-hydroxyphenyl) bicyclo[2.2.1]hept-2-ene, 5-methyl-5-(4-hydroxyphenyl)
bicyclo[2.2.1]hept-2-ene, 8-(4-hydroxyphenyl) tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, and

8-methyl-8-(4-hydroxyphenyl) tetracyclo[4.4.0.12|5.17'l0]dodeca-3-ene. These monomers may be used singly, or two or more thereof may be used in combination. [0065]
Specific examples of the cyclic olefin monomers having non-protonic polar groups include
cyclic olefins having ester groups such as 5-acetoxy bicyclo[2.2.1]hept-2-ene,
5-methoxycarbonyl bicyclo[2.2.1 ]hept-2-ene, 5-methyl-5-methoxycarbonyl
bicyclo[2.2.1 ]hept-2-ene, 8-acetoxy tetracyclo[4.4.0.125.17-1 °]dodeca-3-ene,
8-methoxycarbonyl tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-ethoxycarbonyl
tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-n-propoxycarbonyl
tetracyclo[4.4.0.112-5.17'1 °]dodeca-3-ene, 8-isopropoxycarbonyl
tetracyclo[4.4.0.125.171 °]dodeca-3-ene, 8-n-butoxycarbonyl
tetracyclo[4.4.0.12-5.17'10]dodeca-3-ene, 8-methyl-8-methoxycarbonyl
tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-methyl-8-ethoxycarbonyl
tetracyclo[4.4.0.12,5.17'10]dodeca-3-ene, 8-methyl-8-n-propoxycarbonyl
tetracyclo[4.4.0.12-5.17'10]dodeca-3-ene, 8-methyl-8-isopropoxycarbonyl
tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-methyl-8-n-butoxycarbonyl
tetracyclo[4.4.0.12-5.1710]dodeca-3-ene, 8-(2,2,2-trifluoroethoxycarbonyl)
tetracyclo[4.4.0.12'5.17-10]dodeca-3-ene, and 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl) tetracyclo[4.4.0.12'5.17,10]dodeca-3-ene; cyclic olefins having N-substitute imide groups such as N-phenyl-(5-norbornene-2,3-dicarboxyimide); cyclic olefins having cyano groups such as 8-cyanotetracyclo[4.4.0.125.17 '1 °]dodeca-3-ene,
8-methyl-8-cyanotetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, and
5-cyanobicyclo[2.2.1]hept-2-ene; and cyclic olefins having halogen atoms such as
8-chlorotetracyclo[4.4.0.125.17'10]dodeca-3-ene and
8-methyI-8-chlorotetracyclo[4.4.0.12'5.17'10]dodeca-3-ene. These monomers may be used singly, or two or more thereof may be used in combination. [0066]
Specific examples of the cyclic olefin monomers having no polar groups include
bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene,
5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene,
5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.12'5]deca-3,7-diene,
tetracyclo[8.4.0.111'14.03'7]pentadeca-3,5,7,12,11-pentaene,
tetracyclo[4.4.0.12<5.17-1 °]deca-3-ene, 8-methyl-tetracyclo[4.4.0.12'5.17>1 °]dodeca-3-ene,
8-ethyl-tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-methylidene-tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.12'5.17'l0]dodeca-3-ene, 8-vinyl-tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene, pentacyclo[6.5.1.13-6.02'7.09'13]pentadeca-3,10-diene, cyclopentene, cyclopentadiene,

1,4-methano-1,4,4a, 5,10,1 Oa-hexahydroanthracene,
8-phenyl-tetracyclo[4.4.0.12'5.17'10]dodeca-3-ene,
tetracyc!o[9.2.1.02'10.03'8]tetradeca-3,5,7,12-tetraene,
pentacyclo[7.4.0.13'6.110'13.02'7]pentadeca-4,11-diene, and
pentacyclo[9.2.1.14'7.02'10.03'8]pentadeca-5,12-diene. These monomers may be used singly,
or two or more thereof may be used in combination.
[0067]
Specific examples of non-cyclic-olefin monomers include a-olefins having 2 to 20 carbon
atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene,
3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,
4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and
1-eicosene; and linear olefins such as 1,4-hexadiene, 4-methyl-1,4-hexadiene,
5-methyl-1,4-hexadiene, 1,7-octadiene, and other nonconjugated dienes. These monomers
may be used singly, or two or more thereof may be used in combination.
[0068]
Common methods can be used for the polymerization of cyclic olefin polymers from the
monomers listed above. They include, for example, ring opening polymerization and addition
polymerization.
[0069]
Preferred polymerization catalysts for these methods include, for example, metal complexes
of molybdenum, ruthenium, and osmium. These polymerization catalysts may be used singly
or as a combination of two or more thereof.
[0070]
For the cyclic olefin polymers produced through polymerization of the various monomers,
hydrogenation is performed commonly using a hydrogenation catalyst. Examples of the
hydrogenation catalyst include, for example, those commonly used for hydrogenation of
olefin compounds. Specifically, useful ones include Ziegler type homogeneous catalysts,
noble metal complex catalysts, and supported type noble metal based catalysts.
[0071]
Of these hydrogenation catalysts, noble metal complex catalysts such as of rhodium and
ruthenium are preferable because they will not cause side reactions such as modification of
functional groups and also because the unsaturated carbon-carbon bonds in the polymers
will be hydrogenated selectively. Particularly preferable are highly electron donative,
nitrogen-containing heterocyclic carbene compounds and ruthenium catalysts having
coordinated phosphines.
[0072]
Siloxane resins useful as the alkali-soluble resin (a) include polysiloxanes obtainable
through hydrolysis condensation of at least one compound selected from the organosilanes

represented by general formula (4) given below and the organosilanes represented by
general formula (5) given below. The use of organosilanes represented by general formula
(4) or (5) serves to obtain a photosensitive colored resin composition having a high
sensitivity and resolution.
Organosilanes as represented by general formula (4) that are useful as the alkali-soluble
resin (a) are as defined below.
[0073]
[Chemical compound 6]
(R17)mSi(OR18)4.m (4)
In general formula (4) given above, R17 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R18 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. Here, m is an integer of 0 to 3. When m is 2 or more, the plurality of R17 groups may be identical to or different from each other. When m is 2 or less, the plurality of R18 groups may be identical to or different from each other. [0074]
Specific examples of the organosilanes represented by general formula (4) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; trifunctional silanes such as methyl trimethoxysilane, methyl triethoxysilane, methyl triisopropoxysilane, methyl tri-n-butoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, ethyl triisopropoxysilane, ethyl tri-n-butoxysilane, n-propyl trimethoxysilane, n-propyl triethoxysilane, n-butyl trimethoxysilane, n-butyl triethoxysilane, n-hexyl trimethoxysilane, n-hexyl triethoxysilane, decyl trimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, 3-methacryloyloxy propyl trimethoxysilane, 3-methacryloyloxy propyl triethoxysilane, 3-acryloxy propyl trimethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, p-hydroxyphenyl trimethoxysilane, l-(p-hydroxyphenyl) ethyl trimethoxysilane, 2-(p-hydroxyphenyl) ethyl trimethoxysilane, 4-hydroxy-5-(p-hydroxyphenyl carbonyloxy) pentyl trimethoxysilane, trifluoromethyl trimethoxysilane, trifluoromethyl triethoxysilane, 3,3,3-trifluoropropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 2-(3,4-epoxy cyclohexyl) ethyl triethoxysilane, [(3-ethyl-3-oxetanyl) methoxyjpropyl trimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy]propyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-trimethoxysilyl propyl succinate, 1-naphthyl trimethoxysilane, 1-naphthyl triethoxysilane, 1-naphthyl tri-n-propoxysilane, 2-naphthyl trimethoxysilane, 1-anthracenyl trimethoxysilane, 9-anthracenyl trimethoxysilane, 9-phenanthrenyl trimethoxysilane, 9-fluorenyl trimethoxysilane, 2-fluorenyl trimethoxysilane,

1-pyrenyl trimethoxysilane, 2-indenyl trimethoxysilane, and 5-acenaphthenyl trimethoxysilane; difunctional silanes such as dimethyl dimethoxysilane, dimethyl diethoxysilane, dimethyl diacetoxysilane, di-n-butyl dimethoxysilane, diphenyl dimethoxysilane, (3-glycidoxypropyl) methyl dimethoxysilane, (3-glycidoxypropyI) methyl diethoxysilane, di(l-naphthyl) dimethoxysilane, and di(l-naphthyl) diethoxysilane; and monofunctional silanes such as trimethyl methoxysilane, tri-n-butyl ethoxysilane, (3-glycidoxypropyl) dimethyl methoxysilane, and (3-glycidoxy propyl) dimethyl ethoxysilane. Two or more of these organosilanes may be used in combination. [0075]
Organosilanes as represented by general formula (5) that are useful as the alkali-soluble resin (a) are as defined below. [Chemical compound 7]
OR20
R19O^SKO|— R22 (5)
OR21 n In general formula (5) given above, R19 to R22 each independently denote a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. Here, n denotes a real number in the range of 2 to 8. When n is 2 or more, the plurality of R20 and R21 groups may be identical to or different from each other. [0076]
Specific examples of organosilanes as represented by general formula (5) include Methyl Silicate 51 (R19 to R22: methyl group, n: 4 on average) manufactured by Fuso Chemical Co., Ltd., M Silicate 51 (R19 to R22: methyl group, n: 3 to 5 on average), Silicate 40 (R19 to R22: ethyl group, n: 4 to 6 on average), Silicate 45 (R19 to R22: ethyl group, n: 6 to 8 on average) manufactured by Tama Chemicals Co., Ltd., Methyl Silicate 51 (R19 to R22: methyl group, n: 4 on average), Methyl Silicate 53A (R19 to R22: methyl group, n: 7 on average), and Ethyl Silicate 40 (R19 to R22: ethyl group, n: 5 on average) manufactured by Colcoat Co., Ltd. Two or more of these may be used in combination. [0077]
The content of Si atoms originating from an organosilane as represented by general formula (4) or general formula (5) in a poiysiloxane can be determined by identifying the structure of the original organosilane by 1H-NMR, 13C-NMR, 29Si-NMR, IR, TOF-MS, etc., and calculating the ratio between the integrated value of the peak attributed to the Si-C bond and that attributed to the Si-0 bond in an IR spectrum. [0078]
There are no specific limitations on the weight average molecular weight (Mw) of the poiysiloxane, but the polystyrene based value is preferably 1,000 or more as determined by

GPC (gel permeation chromatography) to ensure improved coatability. From the viewpoint of
solubility in developers, on the other hand, the content is preferably 100,000 or less, more
preferably 50,000 or less.
[0079]
A polysiloxane to be used for the present invention can be synthesized through hydrolysis
and partial condensation of monomers such as organosilanes as represented by general
formula (3) or (4). Here, the partial condensation step is designed so that part of the Si-OH
bonds in the hydrolysate will remain in the resulting polysiloxane, instead of complete
condensation of the Si-OH bonds. Generally known methods can be used for the hydrolysis
and partial condensation. A good method, for example, is to add a solvent and water, plus a
catalyst if necessary, to an organosilane mixture and heating at 50°C to 150°C for about 0.5
to 100 hours while stirring. During the stirring, hydrolysis by-products (alcohols such as
methanol) and condensation by-products (water) may be evaporated by distillation if
necessary.
[0080]
There are no specific limitations on the catalyst, but preferred ones include acid catalysts
and basic catalysts. Specific examples of the acid catalysts include hydrochloric acid, nitric
acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic
acid, multivalent carboxylic acids, anhydrides thereof, and ion exchange resins. Specific
examples of the basic catalysts include triethyl amine, tripropyl amine, tributyl amine,
tripentyl amine, trihexyl amine, triheptyl amine, trioctyl amine, diethyl amine, triethanol amine,
diethanol amine, sodium hydroxide, potassium hydroxide, alkoxysilanes having amino
groups, and ion exchange resins.
[0081]
From the viewpoint of storage stability of the photosensitive resin composition, the
polysiloxane solution obtained after the hydrolysis and partial condensations steps is
preferably free of these catalysts, and therefore the catalysts may preferably be removed as
required. There are no specific limitations on the removal method, but rinsing with water
and/or treatment with ion exchange resin are preferred from the viewpoint of simple
operation and removal performance. In a rinsing step, the polysiloxane solution is diluted
with an appropriate hydrophobic solvent and then rinsed with water a few times, followed by
condensing the resulting organic layer by using, for example, an evaporator. The above
treatment with an ion exchange resin is designed for bringing the polysiloxane solution into
contact with an appropriate ion exchange resin.
[0082]
The photosensitive resin composition used in the cured film according to the present
invention contains a photoacid generating agent (b). A photoacid generating agent (b) is a
compound that generates an acid when exposed to light. Examples of the photoacid
generating agent (b) include quinone diazide compounds, sulfonium salts, phosphonium

salts, diazonium salts, and iodonium salts. [0083]
The quinone diazide compounds include those in the form of a sulfonic acid of quinonediazide ester-bonded to a polyhydroxy compound or a polyamino compound, those in the form of a sulfonic acid of quinonediazide sulfonamide-bonded to a polyhydroxy compound, and those in the form of a sulfonic acid of quinonediazide ester-bonded and/or sulfoneamide-bonded to a polyhydroxypolyamino compound. Of these, naphthoquinone diazide sulfonyl ester compounds are preferable and 4-naphthoquinone diazide sulfonyl ester compounds are particularly preferable. It is preferable that 50 mol% or more of the functional groups in the polyhydroxy compounds and polyamino compounds be substituted by quinone diazide. The use of a quinone diazide compound substituted to 50 mol% or more ensures a decrease in the affinity of the quinone diazide compound with an aqueous alkali solution, a large decrease in the solubility of the unexposed region of the resin composition in the aqueous alkali solution, and conversion of the quinone diazide sulfonyl group to an indene carboxylic acid under light irradiation, which leads to a large dissolution rate of the exposed region of the resin composition in the aqueous alkali solution. As a result, the ratio in dissolution rate between the exposed region and the unexposed region of the composition increases to enable the formation of a pattern with a high resolution. The use of such a quinone diazide compound enables the production of a positive type photosensitive resin composition that is photosensitive to the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a common mercury lamp. [0084]
Here, 4-naphthoquinone diazide sulfonyl ester compounds are absorptive to light in the i-line region of mercury lamps and suitable for i-line exposure, whereas 5-naphthoquinone diazide sulfonyl ester compounds are absorptive to light in a wider region including the g-line of mercury lamps and suitable for g-line exposure. Both 4-naphthoquinone diazide sulfonyl ester compounds and 5-naphthoquinone diazide sulfonyl ester compounds can serve effectively for the present invention, but it is desirable that a suitable 4-naphthoquinone diazide sulfonyl ester compound or 5-naphthoquinone diazide sulfonyl ester compound be selected to suite the wavelength used for exposure. Furthermore, it is possible to produce a naphthoquinone diazide sulfonyl ester compound that containing both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in one molecule, or it may also be effective to use a mixture of a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. [0085]
When using a 4-naphthoquinone diazide sulfonyl ester compound, in particular, the o-quinone diazide compound is decomposed in the heat treatment step and part of the molecules are removed out of the film after being converted into sulfur dioxide or carbon dioxide, thus serving to reduce the acidic gas generation from the cured film. As a result, the

shrinkage of pixels caused by acidic gases is further depressed and accordingly, this
compound is particularly preferred.
[0086]
It is preferable for the photoacid generating agent (b) to account for 1 part by mass or more,
more preferably 3 parts by mass or more, and 40 parts by mass or less, more preferably 30
parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (a). Pattern
formation can be performed with high sensitivity when the quantity is 1 part by mass or more,
whereas the shrinkage of pixels caused by acidic gases from the o-quinone diazide
compound can be depressed to enable the production of an organic EL device with
improved long-term reliability when it is 40 parts by mass or less.
[0087]
The photosensitive resin composition used for the cured film according to the present
invention contains at least one compound (c) selected from the group consisting of cyclic
amides, cyclic ureas, and derivatives thereof. It is considered that if at least one compound
(c) selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof
is contained, the compound (c) works as a quencher for acidic gases to serve to prevent a
decrease in light emission luminance or shrinkage of pixels and provide an organic EL
device having high long-term reliability.
[0088]
Such at least one compound (c) selected from the group consisting of cyclic amides, cyclic
ureas, and derivatives thereof preferably has a structure as represented by general formula
(1) given below and two or more such compounds may be contained together.
[0089]

(In general formula (1), n denotes an integer of 1 to 4, and X denotes CH or a nitrogen atom. R1 and R2 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. However, R1 is an organic group containing 2 to 20 carbon atoms when X is CH, and it is a hydrogen atom or an organic group containing 1 to 20 carbon atoms when X is a nitrogen atom. R2 is a hydrogen atom when X is CH, and it is a hydrogen atom or an organic group containing 1 to 20 carbon atoms when X is a nitrogen atom.) [0090]
The at least one compound (c) selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof preferably has a boiling point of 210°C or more to ensure easy

persistence in the film after the heat treatment. The boiling point is preferably 400°C or less
from the viewpoint of reducing uneven coating. If the boiling point cannot be measured
under atmospheric pressure, a measured value can be converted to the boiling point at
atmospheric pressure using a boiling point conversion table.
[0091]
Specific examples of the cyclic amides, cyclic ureas, and derivatives thereof include
2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone,
N-isopropyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone,
N-pentyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone,
N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone,
N-(2-hydroxyethyl)-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-vinyl-2-pyrrolidone,
N.N'-dimethylpropylene urea, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone,
2-piperidone, and e-caprolactam. Of these, N-cyclohexyl-2-pyrrolidone (boiling point 154°C
at 7 mmHg, converted boiling point at atmospheric pressure 305°C),
N-(2-hydroxyethyl)-2-pyrrolidone (boiling point 175°C at 10 mmHg, converted boiling point at
atmospheric pressure 313°C) are preferred because they are high enough in boiling point to
remain more easily in the film after the heat treatment.
[0092]
The total quantity of the at least one compound (c) selected from the group consisting of
cyclic amides, cyclic ureas, and derivatives thereof accounts for 0.005 mass% or more and 5
mass% or less in 100 parts by mass of the alkali-soluble resin (a). In the photosensitive resin
composition used to form the cured film, the quantity of the compound (c) preferably
accounts for 0.1 part by mass or more, more preferably 1 parts by mass or more, and
preferably 15 parts by mass or less, more preferably 10 parts by mass or less, relative to 100
parts by mass of the alkali-soluble resin (a). A good organic EL device with an increased
long-term reliability can be produced if the compound (c) accounts for 0.1 part by mass or
more, whereas pattern formation can be performed with high sensitivity if it accounts for 15
parts by mass or less.
[0093]
The photosensitive resin composition used to form the cured film according to the present
invention contains a thermal crosslinking agent (d) that contains an epoxy compound,
oxetanyl compound, isocyanate compound, acidic group-containing alkoxymethyl compound,
and/or acidic group-containing methylol compound. A thermal crosslinking agent is a
compound that contains, in one molecule, at least two heat-reactive functional groups such
as alkoxymethyl groups, methylol groups, epoxy groups, and oxetanyl groups.
[0094]
The thermal crosslinking agent (d) that contains an epoxy compound, oxetanyl compound,
isocyanate compound, acidic group-containing alkoxymethyl compound, and/or acidic
group-containing methylol compound is preferred because it is so high in heat resistance as

to permit reduction in outgassing from the cured film and production of an organic EL device
with an increased long-term reliability.
[0095]
Of the various materials for the thermal crosslinking agent, the use of an acidic
group-containing alkoxymethyl compound or an acidic group-containing methylol compound
is particularly preferable. The existence of an acidic group allows the at least one compound
(c) selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof
to remain easily in the film after the heat treatment step to permit the production of an
organic EL device with higher long-term reliability. Examples of the acidic group include
carboxy groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups, of which
phenolic hydroxyl groups are preferred.
[0096]
Preferred examples of the epoxy compounds include, for example, Epolite 40E, Epolite
100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP,
Epolite 80MF, Epolite 4000, Epolite 3002 (all manufactured by Kyoeisha Chemical Co., Ltd.),
Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L (all
manufactured by Nagase ChemteX Corporation), Epikote 828 (manufactured by Japan
Epoxy Resins Co., Ltd.), and NC3000 (manufactured by Nippon Kayaku Co., Ltd.).
[0097]
Preferred examples of the oxetanyl compounds include Etemacoll EHO, Eternacoll OXBP,
Etemacoll OXTP, Eternacoll OXMA (all manufactured by Ube Industries, Ltd.), and
oxetanized phenol novolac.
[0098]
Preferred examples of the isocyanate compounds include, for example, Desmodur
BB1101/1, Desmodur BL3375 (both manufactured by Bayer MaterialScience Ltd.), and
TPA-B80E (manufactured byAsahi Kasei Chemicals Corporation).
[0099]
Preferred examples of the acidic group-containing alkoxymethyl compounds and acidic
group-containing methylol compounds include, for example, DML-PC, DML-34X, DML-PTBP,
DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC,
DML-MTrisPC, DML-BPC, DML-BisOC-P, TriML-P, TriML-35XL, TML-HQ, TML-BP,
TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, and
HMOM-TPHAP (trade names, all manufactured by Honshu Chemical Industry Co., Ltd.).
[0100]
Useful materials for the thermal crosslinking agent (d) that contains an epoxy compound,
oxetanyl compound, isocyanate compound, acidic group-containing alkoxymethyl compound,
and/or acidic group-containing methylol compound may be used as a combination of two or
more thereof.
[0101]

The thermal crosslinking agent (d) that contains an epoxy compound, oxetanyl compound,
isocyanate compound, acidic group-containing alkoxymethyl compound, and/or acidic
group-containing methylol compound preferably accounts for 1 part by mass or more and 30
parts by mass or less relative to 100 parts by mass of the alkali-soluble resin (a). If the
thermal crosslinking agent (d) accounts for 1 part by mass or more and 30 parts by mass or
less, it ensures the formation of a calcined or cured film with increased chemical resistance
and hardness, reduction in outgassing from the cured film, production of an organic EL
display device with increased long-term reliability, and production of a photosensitive resin
composition with high storage stability.
[0102]
The photosensitive resin composition used in the cured film according to the present
invention may contain a phenolic hydroxyl group-containing compound (f). The phenolic
hydroxyl group-containing compound (f) adds to the alkali developability of the
photosensitive resin composition and also serves to allow the at least one compound (c)
selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof to
remain easily in the film.
[0103]
Examples of the phenolic hydroxyl group-containing compounds (f) include, for instance,
Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP,
BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP,
Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA,
TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P,
BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP,
methylene-tris-FR-CR, BisRS-26X, BisRS-OCHP, (trade names, all manufactured by
Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP,
BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade names, all manufactured byAsahi Organic
Chemicals Industry Co., Ltd.), 1,4-dihydroxy naphthalene, 1,5-dihydroxy naphthalene,
1,6-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 2,3-dihydroxy naphthalene,
2,6-dihydroxy naphthalene, 2,7-dihydroxy naphthalene, 2,4-dihydroxy quinoline,
2,6-dihydroxy quinoline, 2,3-dihydroxy quinoxaline, anthracene-1,2,10-triol,
anthracene-1,8,9-triol, and 8-quinolinol.
[0104]
Such a phenolic hydroxyl group-containing compound (f) preferably accounts for 1 part by
mass or more and 30 parts by mass or less relative to 100 parts by mass of the alkali-soluble
resin (a).
[0105]
The photosensitive resin composition used in the cured film according to the present
invention may contain an organic solvent (e). This allows the photosensitive resin
composition to be in a varnish-like state, ensuring improved coatability.

[0106]
Useful examples of the organic solvent (e) include, for example, polar aprotic solvents such as y-butyrolactone; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-phenylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; and aromatic hydrocarbons such as toluene and xylene; which may be used singly or as a mixture thereof. [0107]
There are no specific limitations on the quantity of the organic solvent (e), but it preferably accounts for 100 to 3,000 parts by mass, more preferably 300 to 2,000 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (a). There are no specific limitations on the boiling point of the organic solvent (e), but it is preferable for part of the components of the organic solvent (e) to have a boiling point of 180°C or more. Relative to the total quantity of the organic solvent (e), the solvent components having a boiling point of 180°C or more account for 30 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. If the solvent components having a boiling point of 180°C or more account for 30 parts by mass or less, it serves to reduce the outgassing from planarizing layers or insulation layers in the heat-cured film, resulting in an organic EL device with an increased long-term reliability. [0108] The photosensitive resin composition used in the cured film according to the present

invention may contain an adhesion improving agent. Examples of the adhesion improving agent include silane coupling agents such as vinyl trimethoxysilane, vinyl triethoxysilane, epoxy cyclohexylethyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and N-phenyl-3-aminopropyl trimethoxysilane, and others such as titanium chelating agent, aluminum chelating agent, and those compound resulting from a reaction between an aromatic amine compound and an alkoxy group-containing silicon compound. Two or more of these may be contained together. If these adhesion improving agents are contained, a photosensitive resin film in a development step, for example, can achieve stronger adhesion to a substrate material such as silicon wafer, ITO, Si02, and nitride silicon. They also serve to improve the resistance to oxygen plasma used for cleaning and to UV ozone processing. The content of the adhesion improving agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the alkali-soluble resin (a). [0109]
The photosensitive resin composition used in the cured film according to the present invention may contain a surface active agent to ensure improved wetting of the substrate. [0110]
Examples of the surface active agent include fluorine-based surface active agents such as Fluorad (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by DIC Corporation), and Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); organic siloxane surface active agents such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and BYK (manufactured by BYK-Chemie); and acrylic polymer surface active agents such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). [0111]
Described in detail below is the method for producing the cured film according to the present invention from a photosensitive resin composition. The photosensitive resin composition is spread by the spin coating technique, slit coating technique, dip coating technique, spray coating technique, printing technique, etc., to form a coating film of the photosensitive resin composition. Before the coating step, the base to be coated with the photosensitive resin composition may be pre-treated with an adhesion improving agent as described above. For example, an adhesion improving agent may be dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate to a content of 0.5 to 20 parts by mass, and the resulting solution is then used to treat the surface of the base. The treatment of the surface of the base may be carried out by such a technique as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. After the

photosensitive resin composition spreading step, vacuum drying is carried out if necessary,
followed by heat-treatment in the range of 50°C to 180°C for 1 minute to several hours using
a hot plate, oven, infrared ray, etc., to produce a photosensitive resin film.
[0112]
Described below is the method for forming a pattern from the resulting photosensitive resin
film. An actinic ray is applied to the photosensitive resin film through a mask having an
intended pattern. Actinic rays available for light exposure include ultraviolet ray, visible light,
electron beam, and X-ray, but the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of
mercury lamps are preferred for the invention.
[0113]
After the light exposure step, the exposed region is removed using a developing solution.
Preferable developers include an aqueous solution of alkaline compounds such as
tetramethyl ammonium hydroxide, diethanol amine, diethyl aminoethanol, sodium hydroxide,
potassium hydroxide, sodium carbonate, potassium carbonate, triethyl amine, diethyl amine,
methyl amine, dimethyl amine, dimethylaminoethyl acetate, dimethylaminoethanol,
dimethylaminoethyl methacrylate, cyclohexyl amine, ethylene diamine, and hexamethylene
diamine. In some cases, such an aqueous alkali solution may contain polar solvents such as
N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,
y-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and
isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate;
and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl
ketone; which may be added singly or together with several others selected therefrom. The
available development techniques include spraying, paddling, immersion, and ultrasonic
vibration.
[0114]
The pattern formed by development is preferably rinsed with distilled water. Here again, the
distilled water used for rinsing may contain an alcohol such as ethanol and isopropyl alcohol,
an ester such as ethyl lactate and propylene glycol monomethyl ether acetate, or the like.
[0115]
Next, heat treatment is carried out to produce a cured film. This heat treatment works to
remove the residual solvent and components with low heat resistance, thus serving to
produce a cured film with improved heat resistance, chemical resistance, and reliability. In
particular, when the photosensitive resin composition used to form the cured film according
to the present invention contains an alkali-soluble resin selected from polyimide precursors
and polybenzoxazole precursors, a copolymer thereof, or a copolymer of one thereof with an
polyimide, imide rings or oxazole rings can be formed by heat treatment to ensure
improvement in heat resistance, chemical resistance, and reliability. If the thermal
crosslinking agent contained is a compound having at least two selected from alkoxy methyl
groups, methylol groups, epoxy groups, and oxetanyl groups, thermal crosslinking reaction

can be caused by heat treatment to ensure improvement in heat resistance, chemical resistance, and reliability. This heat treatment is performed for 5 minutes to 5 hours by stepwise heating at selected temperatures or continuous heating-up over a certain selected temperature range. For example, heat treatment may be performed at 150°C and 250°C for 30 minutes each. Or, heating may be performed for 2 hours while linearly increasing the temperature from room temperature to 300°C. For the present invention, heat treatment is performed preferably at 150°C to 400°C, more preferably at 200°C or more and 350°C or less, and still more preferably at 220°C or more and 300°C or less. [0116]
The cured film according to the present invention can be used in an organic EL display device. More specifically, it is used suitably as material for planarizing films and insulation layers in organic EL display elements. In such cases, the area of the openings in an insulation layer per unit area is called the insulation layer opening rate. The cured film according to the present invention can serve more effectively in an organic EL display device with a low insulation layer opening rate to achieve high-definition displaying characteristics. This is because the shrinkage of pixels, which can cause problems, spreads from edges of the pixels. More specifically, in an organic EL device, it is preferable for the organic EL display element to have an insulation layer opening rate of 20% or less in the display area from the viewpoint of enhancing the advantageous effects of the invention. [0117]
The cured film according to the present invention can be used in electronic components such as semiconductor devices and multi-layered circuit boards. More specifically, the cured film according to the present invention is used suitably in semiconductor electronic components, semiconductor devices, etc., to serve as material for semiconductor's passivation film, semiconductor element's protection film, interlaminar insulation film in high-density multi-layered wiring, or interlaminar insulation film between redistribution layers. Electronic devices using the cured film according to the present invention as surface protection film, interlaminar insulation film, etc., include, for example, MRAMs with low heat resistance. This means that the cured film according to the present invention is suitable as material for the surface protection film in MRAMs. In addition to MRAMs, so-called polymer memories (polymer ferroelectric RAM: PFRAM) and phase change memories (phase change RAM: PCRAM, ovonics unified memory: OUM), which are highly expected as next generation memories, will likely adopt novel materials that are lower in heat resistance than conventional memories. Thus, the cured film according to the present invention is also suitable as material for their surface protection film. [0118]
Next, the second embodiment is described in detail.
The positive type photosensitive resin composition according to the present invention includes an alkali-soluble resin (a), a photoacid generating agent (b), at least one compound

(c) selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof,
a thermal crosslinking agent (d), and an organic solvent (e), the thermal crosslinking agent
(d) containing an epoxy compound, oxetanyl compound, isocyanate compound, acidic group-containing alkoxymethyl compound, and/or acidic group-containing methylol compound, the compound (c) accounting for 0.1 part by mass or more and 15 parts by mass or less relative to 100 parts by mass of the alkali-soluble resin (a), and the organic solvent
(e) accounting for 100 to 3,000 parts by mass relative thereto. Each of the components is described below.
[0119]
The alkali-soluble resin (a), a photoacid generating agent (b), at least one compound (c)
selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof, a
thermal crosslinking agent (d), and an organic solvent (e) may be those cited as examples of
the alkali-soluble resin (a), a photoacid generating agent (b), at least one compound (c)
selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof, a
thermal crosslinking agent (d), and an organic solvent (e) to use for the cured film according
to the first embodiment.
[0120]
It is preferable for the photoacid generating agent (b) to account for 1 part by mass or more,
more preferably 3 parts by mass or more, and 40 parts by mass or less, more preferably 30
parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (a). Pattern
formation can be performed with high sensitivity when the quantity is 1 part by mass or more,
whereas the shrinkage of pixels caused by acidic gases from the o-quinone diazide
compound can be depressed to enable the production of an organic EL device with
improved long-term reliability when it is 40 parts by mass or less.
[0121]
The at least one compound (c) selected from the group consisting of cyclic amides, cyclic
ureas, and derivatives thereof preferably accounts for 0.1 part by mass or more, more
preferably 1 part by mass or more, and preferably 15 parts by mass or less, more preferably
10 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (a). A good
organic EL device with an increased long-term reliability can be produced if it accounts for
0.1 part by mass or more, whereas pattern formation can be performed with high sensitivity if
it accounts for 15 parts by mass or less.
[0122]
The thermal crosslinking agent (d) that contains an epoxy compound, oxetanyl compound,
isocyanate compound, acidic group-containing alkoxymethyl compound, and/or acidic
group-containing methylol compound preferably accounts for 1 part by mass or more and 30
parts by mass or less relative to 100 parts by mass of the alkali-soluble resin (a). If the
thermal crosslinking agent accounts for 1 part by mass or more and 30 parts by mass or less,
it ensures the formation of a calcined or cured film with increased chemical resistance and

hardness, reduction in outgassing from the cured film, production of an organic EL display
device with increased long-term reliability, and production of a photosensitive resin
composition with high storage stability.
[0123]
The photosensitive resin composition according to the present invention may contain a
phenolic hydroxyl group-containing compound (f). The phenolic hydroxyl group-containing
compound (f) adds to the alkali developability of the positive type photosensitive resin
composition and also serves to allow the at least one compound (c) selected from the group
consisting of cyclic amides, cyclic ureas, and derivatives thereof to remain easily in the film.
The phenolic hydroxyl group-containing compound (f) may be one cited as an example of
the phenolic hydroxyl group-containing compound (f) to use for the first embodiment.
[0124]
Such a phenolic hydroxyl group-containing compound (f) preferably accounts for 1 part by
mass or more and 30 parts by mass or less relative to 100 parts by mass of the alkali-soluble
resin (a).
[0125]
The positive type photosensitive resin composition according to the present invention
contains an organic solvent (e). This allows the positive type photosensitive resin
composition to be in a varnish-like state, ensuring improved coatability. The organic solvent
(e) may be one cited as an example of the organic solvent (e) to use for the first
embodiment.
[0126]
The organic solvent (e) accounts for 100 to 3,000 parts by mass, preferably 300 to 2,000
parts by mass, relative to 100 parts by mass of the alkali-soluble resin (a). Furthermore,
relative to the total quantity of the organic solvent (e), the solvent components having a
boiling point of 180°C or more account for 30 parts by mass or less, preferably 20 parts by
mass or less, and more preferably 10 parts by mass or less. If the solvent components
having a boiling point of 180°C or more account for 30 parts by mass or less, it serves to
reduce the outgassing from planarizing layers or insulation layers in the heat-cured film,
resulting in an organic EL device with an increased long-term reliability.
[0127]
The photosensitive resin composition according to the present invention may contain an
adhesion improving agent. The adhesion improving agent may be one cited as an example
of the adhesion improving agent to use for the first embodiment. The adhesion improving
agent preferably accounts for 0.01 to 15 parts by mass relative to 100 parts by mass of the
alkali-soluble resin (a).
[0128]
The photosensitive resin composition according to the present invention may contain a
surface active agent to ensure efficient wetting of the substrate. The surface active agent

may be one cited as an example of the surface active agent to use for the first embodiment.
[0129]
The method to use for producing a cured film from the photosensitive resin composition
according to the present invention may be one cited as an example of the cured film
production method to use for the first embodiment.
EXAMPLES
[0130]
The present invention will be illustrated below in greater detail with reference to Examples,
but it should be understood that the invention is not construed as being limited thereto. The
evaluations of positive type photosensitive resin composition samples described in
Examples are carried out by the following methods.
[0131]
(1) Preparation of developed film for sensitivity evaluation
A varnish sample was spread over an 8-inch silicon wafer by the spin coating technique
using a coating and developing apparatus (Mark-7, manufactured by Tokyo Electron Ltd.)
and baked on a hot plate at 120°C for 3 minutes to prepare a prebaked film with a film
thickness of 3.0 urn. Subsequently, using a light exposure machine (NSR-2005i9C i-line
stepper, manufactured by Nicon Corporation), it was exposed to light through a mask having
a 10 urn contact hole pattern to an exposure of 100 to 1200 mJ/cm2 in steps of 50 mJ/cm2.
After the light exposure step, using the Mark-7 developing apparatus, it was developed with
an aqueous solution containing 2.38 parts by mass of tetramethyl ammonium (hereinafter
referred to as 2.38% TMAH, manufactured by Tama Chemicals Co., Ltd.) for a time period
required for the film loss caused by development to reach 0.5 urn, followed by rinsing with
distilled water and drying by shaking off water to provide a developed film having a pattern.
[0132]
Method for measurement of film thickness
Measurements were taken using Lambda Ace STM-602 manufactured by Dainippon Screen
Mfg. Co., Ltd. assuming a refractive index of 1.63.
[0133]
Calculation of sensitivity
The pattern of the developed film obtained by the above procedure was observed by an FDP
microscope (MX61, manufactured by Olympus Corporation) at a magnification of 20 times to
determine the minimum exposure required to form contact holes with an opening diameter of
10 urn, which was assumed to represent the sensitivity.
[0134]
Coatability evaluation
The prebaked film prepared by the above procedure was observed visually under light from
a sodium vapor lamp to determine the coatability. The observation was represented by O if
the film was completely uniform, by A if a little uneven, or by x if uneven over the entire

film. [0135]
(2) Calculation of total quantity of compound (c) in cured film
A varnish sample was spread over an 8-inch silicon wafer by the spin coating technique
using a coating and developing apparatus (Mark-7, manufactured by Tokyo Electron Ltd.)
and baked on a hot plate at 120°C for 3 minutes to prepare a prebaked film with a film
thickness of 3.2 urn. After this, using the Mark-7 developing apparatus, it was developed with
an aqueous solution containing 2.38 parts by mass of tetramethyl ammonium (hereinafter
referred to as 2.38% TMAH, manufactured by Tama Chemicals Co., Ltd.) for a time period
required for the film loss caused by development to reach 0.5 urn, followed by rinsing with
distilled water, drying by shaking off water, and curing the developed solid film in a nitrogen
atmosphere in an oven at a predetermined temperature for 60 minutes to provide a cured
film.
[0136]
The film thickness of the resulting cured film was measured, and a 1 x 5 cm portion was cut
out and subjected to an adsorption and capture step using the purge and trap technique.
More specifically, the cured film specimen taken above was heated at 400°C for 60 minutes
using helium as purge gas, and the desorbed components were captured in an adsorption
pipe.
[0137]
Using a thermal desorption apparatus, the captured components were subjected to thermal
desorption under the primary desorption conditions of 260°C for 15 minutes and the
secondary adsorption and desorption conditions of -27°C and 320°C for 5 minutes, followed
by GC-MS analysis using a GC-MS apparatus (7890/5975C, manufactured by Agilent) under
the conditions of a column temperature of 40°C to 300°C, use of helium as carrier gas (1.5
mL/min), and a scan range of m/Z 29 to 600. Each component of the compound (c) was
subjected to GC-MS analysis under the same conditions as above to produce a calibration
curve, and the quantity of gas generation was calculated.
[0138]
The value obtained (ug) was divided by the area of 5 cm2 to give a quotient in ug/cm2. The
quotient was divided by the product of the specific gravity of the alkali-soluble resin (a) and
the film thickness and multiplied by 100 to calculate the total content of the compound (c) in
the cured film.
[0139]
(3) Long-term reliability test of organic EL display device
Production method for organic EL display device
Fig. 1 shows a schematic view of the substrate used. First, a 38 x 46 mm non-alkali glass substrate 1 was coated, by the spin coating technique, with a varnish sample containing the positive type photosensitive resin composition prepared in each Example as specified in

Table 1, and then prebaked on a hot plate at 120°C for 2 minutes. This film was subjected to UV light exposure through a photomask and developed with a 2.38% TMAH solution to dissolve only the light-exposed region, followed by rinsing with pure water. The resulting polyimide precursor pattern was cured in a nitrogen atmosphere in an oven at an predetermined temperature for 60 minutes. In this way, a planarizing layer 2 was formed only in a limited effective area of the substrate (Fig. 1(a)). The planarizing layer 2 had a thickness of about 2.0 urn. Then, a 100 nm APC alloy (Ag alloy) film was formed by the sputtering technique over the entire substrate and etched to serve as a reflecting electrode 3 (Fig. 1(b)). Subsequently, a 10 nm transparent electrically conductive film of indium tin oxide (ITO) was formed by the sputtering technique over the entire substrate and etched to serve as first electrode 4. In addition, an auxiliary electrode 5, which would serve to produce a second electrode 8, was formed simultaneously (Fig. 1 (c)). The resulting substrate was subjected to ultrasonic cleaning for 10 minutes in Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Corporation) and then washed with ultrapure water. In each Example, the entire surface of this substrate was coated, by the spin coating technique, with a varnish sample containing the positive type photosensitive resin composition prepared in each Example as specified in Table 1, and prebaked on a hot plate at 120°C for 2 minutes. This film was subjected to UV light exposure through a photomask and developed with a 2.38% TMAH solution to dissolve only the light-exposed region, followed by rinsing with pure water. The resulting polyimide precursor pattern was cured in a nitrogen atmosphere in an oven at 250°C for 60 minutes. In this way, an insulation layer 6 of photosensitivity polyimide having a structure in which openings each with a width of 70 um and a length of 260 urn were aligned at intervals of 155 um in the width direction and 465 um in the length of direction, wherein each opening served to expose a first electrode 4, was formed only in an limited effective area of the substrate (Fig. 1 (d)). These openings produced above will finally form light emitting pixels. The limited effective area of the substrate had a size of 16 mm * 16 mm and the insulation layer 6 had a thickness of about 2.0 um. [0140]
Then, an organic EL display device was produced using a substrate having a planarizing layer 2, a reflecting electrode 3, a first electrode 4, and an insulation layer 6 formed thereon. After carrying out nitrogen plasma treatment as pre-treatment, an organic EL layer 7 that included a light emitting layer was formed by the vacuum deposition technique (Fig. 1 (e)). Here, the degree of vacuum used in the deposition step was 1 x 10"3 Pa or less and the substrate was rotated relative to the deposition source during the deposition step. First, a compound (HT-1) was deposited to 10 nm to form a hole injection layer and a compound (HT-2) was deposited to 50 nm to form a hole transport layer. Subsequently, a compound (GH-1) and a compound (GD-1) were deposited as host material and dopant material, respectively, on the light emitting layer in such a manner as to achieve a doping concentration of 10 wt% and a thickness of 40 nm. Then, a 40 nm thick layer of compounds

(ET-1) and (LiQ) combined at a volume ratio of 1:1, adopted as electron transport materials, was formed thereon. The structures of the compounds used in the organic EL layer 7 are shown blow. [0141]

[0142]
Then, a compound (LiQ) was deposited to 2 nm and MgAg, mixed at a volume ratio of 10:1,
was deposited to 10 nm to form a second electrode 8 (Fig. 1 (f)). Finally, in a low-humidity
nitrogen atmosphere, a cap-shaped glass plate was adhered with an epoxy resin based
adhesive to achieve sealing, thus producing four 5 mm x 5 mm light emitting devices on one
substrate. The film thickness referred to herein is the reading on a crystal oscillation type film
thickness monitor.
[0143]
Long-term reliability test of organic EL display device
The organic EL display device produced above was placed, with the light emitting face up,
on a hot plate heated at 80°C and exposed to UV light with a wavelength of 365 nm at an
illuminance of 0.6 mW/cm2. After an elapsed time of 250 hours, 500 hours, 1000 hours, or
1500 hours, the device was driven for light emission by a direct current of 10 mA/cm2 and
the light emission area in light emitting pixels was measured.
[0144]
Synthesis example 1: synthesis of hydroxyl group-containing diamine compounds

First, 18.3 g (0.05 mole) of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 ml_ of acetone and 17.4 g (0.3 mole) of propylene oxide, and cooled to -15°C. Then, a solution of 20.4 g (0.11 mole) of 3-nitrobenzoyI chloride dissolved in 100 mL of acetone was added dropwise. After the end of dropping, the solution was allowed to react at -15°C for 4 hours, followed by allowing it to return to room temperature. The resulting white solid precipitate was separated out by filtration and vacuum-dried at 50°C. [0145]
A 30 g portion of the solid material was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by adding 2 g of 5% palladium-carbon. Then, a balloon was used to introduce hydrogen to cause a reduction reaction at room temperature. After about 2 hours, the reaction was finished after checking that the balloon would be deflated no more. After the end of the reaction, the solution was filtrated to remove the palladium compound used as catalyst and concentrated in a rotary evaporator to provide a hydroxyl group-containing diamine compound as represented by the formula given below. [0146]

Synthesis example 2: synthesis of alkali-soluble resin (A-1)
In a dry nitrogen flow, 31.0 g (0.10 mole) of 3, 3', 4, 4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methyl-2-pyrrolidone (NMP). Here, 45.35 g (0.075 mole) of the hydroxyl group-containing diamine compound prepared in Synthesis example 1 and 1.24 g (0.005 mole) of 1,3-bis(3-aminopropyl) tetramethyl disiloxane were added together with 50 g of NMP, followed by performing reaction at 20°C for 1 hour and additional reaction at 50°C for 2 hours. Then, 4.36 g (0.04 mole) of 4-aminophenol, used as end-capping agent, was added together with 5 g of NMP, followed by performing reaction at 50°C for 2 hours. Subsequently, a solution prepared by diluting 28.6 g (0.24 mole) of N,N-dimethylformamide dimethylacetal with 50 g of NMP was added dropwise over 10 minutes. After the dropping, stirring was performed at 50°C for 3 hours. After the stirring, the solution was cooled to room temperature and then the solution was poured into 3 L of water to provide a white precipitate. This precipitate was collected by filtration, rinsed with water three times, and dried in a vacuum drying machine at 80°C for 24 hours to provide a polyimide precursor, that is, the intended alkali-soluble resin (A-1).

[0148]
Synthesis example 3: synthesis of alkali-soluble resin (A-2)
In a dried nitrogen flow, 29.3 g (0.08 mole) of BAHF, 1.24 g (0.005 mole) of
1,3-bis(3-aminopropyl) tetramethyl disiloxane, and 3.27 g (0.03 mole) of 3-aminophenol,
which was used as end capping agent, were dissolved in 150 g N-methyl-2-pyrrolidone
(NMP). To this solution, 31.0 g (0.1 mole) of ODPA was added together with 50 g of NMP,
stirred at 20°C for 1 hour, and additionally stirred at 50°C for 4 hours. Subsequently, 15 g of
xylene was added and stirred at 150°C for 5 hours while distilling water together with xylene.
After the stirring, the solution was poured in 3 L of water and the resulting white precipitate
was collected. This precipitate was collected by filtration, rinsed with water three times, and
dried in a vacuum drying machine at 80°C for 24 hours to provide a polyimide, that is, the
alkali-soluble resin (A-2).
[0149]
Synthesis example 4: synthesis of alkali-soluble resin (A-3)
In a dry nitrogen flow, 18.3 g (0.05 mole) of BAHF was dissolved in 50 g of NMP and 26.4 g
(0.3 mole) of glycidyl methyl ether, and the temperature of the solution was decreased to
-15°C. Then a solution prepared by dissolving 7.4 g (0.025 mole) of diphenyl ether
dicarboxylic acid dichloride (manufactured by Nihon Nohyaku Co., Ltd.) and 5.1 g (0.025
mole) of isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25
g of y-butyrolactone (GBL) was added dropwise while maintaining the internal temperature
at or below 0°C. After the completion of the dropping step, stirring was continued at -15°C for
6 hours. After the end of the reaction, the solution was poured in 3 L of water containing 10
parts by mass of methanol and the resulting white precipitate was collected. This precipitate
was collected by filtration, rinsed with water three times, and dried in a vacuum drying
machine at 80°C for 24 hours to provide a polybenzoxazole precursor, that is, the intended
alkali-soluble resin (A-3).
[0150]
Synthesis example 5: synthesis of alkali-soluble resin solution (A-4)
In a 500 ml flask, 5 g of 2,2'-azobis(isobutyronitrile), 5 g of t-dodecane thiol, and 150 g of
propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) were fed.
Subsequently, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of
tricyclo[5.2.1.02'6]decane-8-yl methacrylate were added and stirred for a while at room
temperature, followed by filling the flask with nitrogen and stirring while heating at 70°C for 5
hours. Then, 15 g of glycidyl methacrylate, 1 g of dimethylbenzyl amine, and 0.2 g of
p-methoxyphenol were add to the resulting solution, followed by stirring while heating at
90°C for 4 hours to provide an acrylic resin solution (A-4). The resulting acrylic resin solution
(A-4) had a solid content of 43 parts by mass.
[0151]
Synthesis example 6: synthesis of quinone diazide compound (B-1)

In a dry nitrogen flow, 21.22 g (0.05 mole) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mole) of 5-naphthoquinone diazide sulfonyl acid chloride were dissolved in 450 g of 1,4-dioxane and maintained at room temperature. To this solution, a mixture of 15.18 g of triethyl amine with 50 g of 1,4-dioxane was added dropwise while maintaining the system below 35°C. After the dropping, stirring was performed at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured in water. Then, the precipitate deposited was collected by filtration. The resulting precipitate was dried in a vacuum drying machine to provide a quinone diazide compound (B-1) as represented by the following formula. [Chemical compound 11]

Synthesis example 7: synthesis of quinone diazide compound (B-2) In a dry nitrogen flow, 21.22 g (0.05 mole) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mole) of 4-naphthoquinone diazide sulfonyl acid chloride were dissolved in 450 g of 1,4-dioxane and maintained at room temperature. To this solution, a mixture of 15.18 g of triethyl amine with 50 g of 1,4-dioxane was added dropwise while maintaining the system below 35°C. After the dropping, stirring was performed at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured in water. Then, the precipitate deposited was collected by filtration. The resulting precipitate was dried in a vacuum drying machine to provide a quinone diazide compound (B-2) as represented by the following formula. [Chemical compound 12]

Reference example 1
First, 10.0 g of the alkali-soluble resin (A-1) prepared in Synthesis example 2, 1.2 g of the
quinone diazide compound (B-1) prepared in Synthesis example 6, 0.1 g of N,N-dimethyl
formamide (C-1 in Tables), adopted as the at least one compound (c) selected from the
group consisting of cyclic amides, cyclic ureas, and derivatives, 2 g of NC3000 (D-1 in
Tables), adopted as the thermal crosslinking agent (d), were dissolved in 30.0 g of propylene
glycol monomethyl ether and 8.0 g of y-butyrolactone, together adopted as the organic
solvent (e), were filtrated through a 0.2 urn polytetrafluoroethylene filter (manufactured by
Sumitomo Electric Industries, Ltd.) to provide a positive type photosensitive resin
composition (varnish) a. Using this varnish a, a developed film, cured film, and organic EL
display device intended for sensitivity evaluation were prepared by the above procedure and
subjected to sensitivity evaluation and evaluation of the long-term reliability of the organic EL
display device. In this procedure, curing was performed at 250°C.
[0155]
Reference examples 2 to 16
Varnishes b to p were prepared by the same procedure as in Reference example 1 using the
compounds listed in Table 1 in the quantities specified therein. Using each of these
varnishes b to p, a developed film, cured film, and organic EL display device intended for
sensitivity evaluation were prepared by the above procedure and subjected to sensitivity
evaluation, determination of the total content of the compound (c) in the cured film, and
evaluation of the long-term reliability of the organic EL display device. In this procedure,
curing was performed at the temperatures specified in Table 1. For Reference examples of
adjacent numbers, those cells containing the same data for the type of varnish used for
forming planarizing layers and insulation layers (positive type photosensitive resin
composition) or curing temperatures are combined into one cell for easy understanding. The
names and structures of the compounds included in Table 1 are as follows.
A-1: alkali-soluble resin (A-1) obtained in Synthesis example 2
A-2: alkali-soluble resin (A-2) obtained in Synthesis example 3
A-3: alkali-soluble resin (A-3) obtained in Synthesis example 4
A-4: alkali-soluble resin (A-4) obtained in Synthesis example 5
B-1: quinone diazide compound (B-1) obtained in Synthesis example 6
B-2: quinone diazide compound (B-2) obtained in Synthesis example 7
C-1: N,N-dimethyl formamide (boiling point 153°C)
C-2: N,N-dimethyl isobutylamide (boiling point 198°C)
C-3: 3-methoxy-N,N-dimethyl propioneamide (boiling point 216°C)
C-4: 3-butoxy-N,N-dimethyl propioneamide (boiling point 252°C)
C-5: stearate amide (boiling point 250°C/12 mmHg, converted boiling point at atmospheric
pressure 412°C)
D-1: NC3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), epoxy compound

adopted as thermal crossiinking agent (d)
D-2: HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.),
acidic group-containing alkoxymethyl compound adopted as thermal crossiinking agent (d)
F: BIR-PC (trade name, manufactured by Asahi Organic Chemicals Industry Co., Ltd.),
phenolic hydroxyl group-containing compound (f)
Evaluation results obtained in Reference examples 1 to 16 are shown in Table 1.
[0156]
[Table 1]

[0156]
Examples 1 to 41
Varnishes A to Q were prepared by the same procedure as in Reference example 1 using
the compounds listed in Tables 2 to 4 in the quantities specified therein. Using each of these
varnishes A to Q, a developed film, cured film, and organic EL display device intended for
sensitivity evaluation were prepared by the above procedure and subjected to sensitivity
evaluation, determination of the total content of the compound (c) in the cured film, and
evaluation of the long-term reliability of the organic EL display device. In this procedure,
curing was performed at the temperatures specified in Tables 2 to 4. For Examples of
adjacent numbers, those cells containing the same data for the type of varnish used for
forming planarizing layers and insulation layers (positive type photosensitive resin
composition) or curing temperatures are combined into one cell for easy understanding. The
names and structures of the compounds included in Tables 2 to 4 are as follows.
(Descriptions of the compounds included in Table 1 are omitted.)
C-6: N-methyl-2-pyrrolidone (boiling point 203°C)
C-7: 1,3-dimethyl-2-imidazolidinone (boiling point 220°C)
C-8: N-cyclohexyl-2-pyrrolidone (boiling point 154°C/7 mmHg, converted boiling point at
atmospheric pressure 305°C)
C-9; N-(2-hydroxyethyl)-2-pyrrolidone (boiling point : 175°C/10 mmHg, converted boiling
point at atmospheric pressure 313°C)
Evaluation results obtained in Examples 1 to 41 are shown in Tables 2 to 4.
[0156]
[0157]
[Table 2]

[0160]
Comparative examples 1 to 9
Varnishes G and R to X were prepared by the same procedure as in Reference example 1
using the compounds listed in Table 5 in the quantities specified therein. Using each of these
varnishes G and R to X, a developed film, cured film, and organic EL display device intended
for sensitivity evaluation were prepared by the above procedure and subjected to sensitivity
evaluation, determination of the total content of the compound (c) in the cured film, and
evaluation of the long-term reliability of the organic EL display device. In this procedure,
curing was performed at the temperatures specified in Table 5. For Examples of adjacent
numbers, those cells containing the same data for the type of varnish used for forming
planarizing layers and insulation layers (positive type photosensitive resin composition) or
curing temperatures are combined into one cell for easy understanding. The names and
structures of the compounds included in Table 5 are as follows. (Descriptions of the
compounds included in Tables 1 to 4 are omitted.)
C-10: aniline (boiling point 184°C), not suitable as compound (c)
C-11: 1-methylimidazole (boiling point 198°C), not suitable as compound (c)
D'-3: NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.),
melamine-based thermal crosslinking agent, not suitable as thermal crosslinking agent (d)
Evaluation results obtained in Comparative examples 1 to 9 are shown in Table 5.
[0161]
[Table 5]
48

EXPLANATION OF NUMERALS
[0162]
1: glass substrate
2: planarization layer
3: reflecting electrode
4: first electrode
5: auxiliary electrode
6: insulation layer
7: organic EL layer
8: second electrode

50

[Claim 1]
Cured film comprising a cured product of a photosensitive resin composition including an
alkali-soluble resin (a), a photoacid generating agent (b), at least one compound (c) selected
from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof, and a
thermal crosslinking agent (d), the thermal crosslinking agent (d) containing an epoxy
compound, oxetanyl compound, isocyanate compound, acidic group-containing
alkoxymethyl compound, and/or acidic group-containing methylol compound, and the total
content of the compound (c) in the cured film being 0.005 mass% or more and 5 mass% or
less.
[Claim 2]
A cured film as set forth in claim 1, wherein the compound (c) has a boiling point of 210°C or
more.
[Claim 3]
A cured film as set forth in claim 2, wherein the compound (c) has a boiling point of 210°C or
more and 400°C or less.
[Claim 4]
A cured film as set forth in any one of claims 1 to 3, wherein the compound (c) has a
structure as represented by general formula (1):
[Chemical compound 11
wherein in general formula (1), n denotes an integer of 1 to 4; X denotes CH or a nitrogen
atom; and R1 and R2 each independently represent a hydrogen atom or an organic group
having 1 to 20 carbon atoms, R1 being an organic group containing 2 to 20 carbon atoms
when X is CH, and being a hydrogen atom or an organic group containing 1 to 20 carbon
atoms when X is a nitrogen atom, and R2 being a hydrogen atom when X is CH, and being a
hydrogen atom or an organic group containing 1 to 20 carbon atoms when X is a nitrogen
atom.
[Claim 5]
A cured film as set forth in any one of claims 1 to 4, wherein the compound (c) includes
N-cyclohexylpyrrolidone and/or N-(2-hydroxyethyl)-2-pyrrolidone.
[Claim 6]
A cured film as set forth in any one of claims 1 to 5, wherein the alkali-soluble resin (a)
includes a polyimide precursor, polyimide, polybenzoxazole precursor, polybenzoxazole,

and/or copolymer thereof.
[Claim 7]
A cured film as set forth in any one of claims 1 to 6, wherein the thermal crosslinking agent
(d) includes an acidic group-containing alkoxymethyl compound and/or an acidic
group-containing methylol compound.
[Claim 8]
A cured film as set forth in any one of claims 1 to 7, wherein the photoacid generating agent
(b) includes a 4-naphthoquinone diazide sulfonyl ester compound.
[Claim 9]
A cured film as set forth in any one of claims 1 to 8 further comprising a phenolic hydroxyl
group-containing compound (f).
[Claim 10]
An organic EL display element comprising a cured film as set forth in any one of claims 1 to
9.
[Claim 11]
An organic EL display element as set forth in claim 10, wherein the opening rate of the cured
film in the display area is 20% or less.
[Claim 12]
A semiconductor electronic component or a semiconductor device comprising a cured film
as set forth in any one of claims 1 to 9 to serve as an interlaminar insulation film between
redistribution layers.
[Claim 13]
A positive type photosensitive resin composition comprising an alkali-soluble resin (a), a
photoacid generating agent (b), at least one compound (c) selected from the group
consisting of cyclic amides, cyclic ureas, and derivatives thereof, a thermal crosslinking
agent (d), and an organic solvent (e), the thermal crosslinking agent (d) containing an epoxy
compound, oxetanyl compound, isocyanate compound, acidic group-containing
alkoxymethyl compound, and/or acidic group-containing methylol compound, the compound
(c) accounting for 0.1 part by mass or more and 15 parts by mass or less relative to 100
parts by mass of the alkali-soluble resin (a), and the organic solvent (e) accounting for 100 to
3,000 parts by mass relative thereto.
[Claim 14]
A positive type photosensitive resin composition as set forth in claim 13, wherein the
compound (c) has a boiling point of 210°C or more.
[Claim 15]
A positive type photosensitive resin composition as set forth in claim 14, wherein the
compound (c) has a boiling point of 210°C or more and 400°C or less.
[Claim 16]
A positive type photosensitive resin composition as set forth in any one of claims 13 to 15,

wherein the compound (c) has a structure as represented by general formula (1):

wherein in general formula (1), n denotes an integer of 1 to 4; X denotes CH or a nitrogen
atom; and R1 and R2 each independently represent a hydrogen atom or an organic group
having 1 to 20 carbon atoms, R1 being an organic group containing 2 to 20 carbon atoms
when X is CH, and being a hydrogen atom or an organic group containing 1 to 20 carbon
atoms when X is a nitrogen atom, and R2 being a hydrogen atom when X is CH, and being a
hydrogen atom or an organic group containing 1 to 20 carbon atoms when X is a nitrogen
atom.
[Claim 17]
A positive type photosensitive resin composition as set forth in any one of claims 13 to 16,
wherein the compound (c) includes N-cyclohexylpyrrolidone and/or
N-(2-hydroxyethyl)-2-pyrrolidone.
[Claim 18]
A positive type photosensitive resin composition as set forth in any one of claims 13 to 17,
wherein the alkali-soluble resin (a) includes a polyimide precursor, polyimide,
polybenzoxazole precursor, polybenzoxazole, and/or copolymer thereof.
[Claim 19]
A positive type photosensitive resin composition as set forth in any one of claims 13 to 18,
wherein the thermal crosslinking agent (d) includes an acidic group-containing alkoxymethyl
compound and/or an acidic group-containing methylol compound.
[Claim 20]
A positive type photosensitive resin composition as set forth in any one of claims 13 to 19,
wherein the photoacid generating agent (b) includes a 4-naphthoquinone diazide sulfonyl
ester compound.
[Claim 21]
A positive type photosensitive resin composition as set forth in any one of claims 13 to 20
further comprising a phenolic hydroxyl group-containing compound (f).
[Claim 22]
A production method for a cured film comprising a step for spreading a positive type
photosensitive resin composition as set forth in any one of claims 13 to 20 over a substrate
to form a photosensitive resin film, a step for drying the photosensitive resin film, a step for
exposing the dried photosensitive resin film to light, a step for developing the light-exposed

photosensitive resin film, and a step for heat-treating the developed photosensitive resin
film.
[Claim 23]
A production method for a cured film as set forth in claims 22, wherein the step for
heat-treating the developed photosensitive resin film uses a heat-treating temperature of
220°C or more and 300°C or less.