阅读说明：本技术 感光性树脂组合物、感光性树脂片、固化膜及其制造方法、有机el显示装置及电子部件 (Photosensitive resin composition, photosensitive resin sheet, cured film, method for producing cured film, organic EL display device, and electronic component ) 是由 小森悠佑 鹫见岳 三好一登 于 2020-03-04 设计创作，主要内容包括：本发明的课题是提供即使在200℃以下的温度下进行了烧成的情况下酰亚胺化率也良好,图案加工性高,将固化膜使用于有机EL显示装置时的长期可靠性高的感光性树脂组合物。为了解决上述课题,本发明的感光性树脂组合物含有聚酰亚胺前体(a)、具有吸电子性基的酚化合物(b)、和感光性化合物(c),该聚酰亚胺前体(a)具有来源于电离电位小于7.1eV的二胺的残基。(The invention provides a photosensitive resin composition which has good imidization rate even if being fired at a temperature of 200 ℃ or lower, high pattern processability and high long-term reliability when a cured film is used in an organic EL display device. In order to solve the above problems, the photosensitive resin composition of the present invention contains a polyimide precursor (a) having a residue derived from a diamine having an ionization potential of less than 7.1eV, a phenol compound (b) having an electron-withdrawing group, and a photosensitive compound (c).)

1. A photosensitive resin composition comprising a polyimide precursor (a) having a residue derived from a diamine having an ionization potential of less than 7.1eV, a phenol compound (b) having an electron-withdrawing group, and a photosensitive compound (c).

2. The photosensitive resin composition according to claim 1, wherein the content of the residue derived from a diamine having an ionization potential of less than 7.1eV is 5 to 50 mol% based on 100 mol% of the diamine residues constituting the polyimide precursor (a).

3. The photosensitive resin composition according to claim 1 or 2, wherein the residue derived from a diamine having an ionization potential of less than 7.1eV has an ether bond.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the diamine having an ionization potential of less than 7.1eV comprises 1 or more diamines selected from the group consisting of 4, 4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [4- (4-aminophenoxy) phenyl ] propane, and 1, 3-bis (4-aminophenoxy) benzene.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the content of the phenol compound (b) having an electron-withdrawing group is 1 to 50 parts by mass relative to 100 parts by mass of the polyimide precursor (a).

6. The photosensitive resin composition according to any one of claims 1 to5, wherein the phenol compound (b) having an electron-withdrawing group contains a compound (b1) having a phenolic hydroxyl group with a pKa of 11.0 or less.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the phenol compound (b) having an electron-withdrawing group comprises a compound (b2) represented by general formula (1),

in the general formula (1), A represents a 2-valent group selected from each structure shown in the general formula (2), a and b each independently represent an integer of 0 to 3, and a + b is an integer of 2 to 4; in the general formula (2), R¹And R²Each independently represents a halogen atom or a 1-valent organic group having 1 to 20 carbon atoms substituted with a halogen atom.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising a colorant (d).

9. A photosensitive resin sheet comprising the photosensitive resin composition according to any one of claims 1 to 8.

10. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive resin sheet according to claim 9.

11. A method for producing a cured film, comprising the steps of: forming a photosensitive resin film made of the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive resin sheet according to claim 9 on a substrate; exposing the photosensitive resin film to light; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film at 200 ℃ or lower.

12. A method for producing a cured film, comprising the steps of: forming a photosensitive resin film made of the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive resin sheet according to claim 9 on a substrate; exposing the photosensitive resin film to light; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film in an atmosphere having an oxygen concentration of 1% or more.

13. An organic EL display device comprising a driving circuit, a planarizing layer, a1 st electrode, an insulating layer, a light-emitting layer, and a 2 nd electrode on a substrate, wherein the planarizing layer and/or the insulating layer comprises the cured film according to claim 10.

14. The organic EL display device according to claim 13, wherein the planarization layer is composed of 2 to5 layers.

15. An electronic component comprising an electrode and a metal wiring on a substrate, and further comprising an interlayer insulating layer and/or a surface protective layer, wherein the cured film according to claim 10 is provided on at least a part of the interlayer insulating layer and/or the surface protective layer.

Technical Field

The present invention relates to a photosensitive resin composition which can be suitably used for a planarization layer, an insulating layer of an organic EL display device, an interlayer insulating layer of an electronic component, a surface protective layer, and the like.

Background

In display devices having a thin display such as a smartphone, a tablet PC, and a television, a large number of products using an organic electroluminescence (hereinafter, "organic EL") display device have been developed. In general, an organic EL display device includes a driver circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode over a substrate, and can emit light by applying a voltage between the first electrode and the second electrode which face each other. Among them, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for planarization layers and insulating layers. Among these, a photosensitive resin composition using a polyimide-based resin is suitably used in order to provide a highly reliable organic EL display device because the resin has high heat resistance and a gas component generated from a cured film is small.

Generally, a coating film of a precursor of polyimide is subjected to thermal dehydration ring closure to obtain a polyimide film having excellent heat resistance and mechanical propertiesA film of properties. In this case, high-temperature firing at 300 ℃ or higher is generally required. However, for example, in an Organic EL display device of a white OLED (Organic Light Emitting Diode) and color filter system, a low-temperature curing process is required in a post-process because the heat resistance of a color filter is low. Further, polyimide, polybenzeneAzoles are also widely used as surface protective layers, interlayer insulating layers, and the like of semiconductor devices. However, for example, MRAM (Magnetoresistive Memory) and sealing resin, which are expected to be next-generation memories, are not resistant to high temperature. Therefore, for the insulating layer, the planarizing layer, and the protective layer used for such an element, a polyimide resin is required which has a good imidization ratio even when cured by firing at a low temperature of 200 ℃ or lower and which has characteristics comparable to those of conventional materials fired at a high temperature of about 300 ℃.

As a technique for lowering the temperature of imidization, a negative photosensitive resin composition containing a polyimide precursor having a weight average molecular weight of 3000 or more and less than 16000 and having a specific structure in place of a carboxyl group of a polyamic acid and a photopolymerization initiator is disclosed (see patent document 1). In addition to a technique of adding a catalytic amount of p-toluenesulfonic acid, which is a known strong acid, to a polyamic acid solution, a technique of adding a catalytic amount of 1, 4-diazabicyclo [2.2.2] octane or 1, 8-diazabicyclo [5.4.0] -7-undecene, which is a strong base, to a polyamic acid solution has been disclosed (see non-patent document 1). By using a strong acid or a strong base as the imidization accelerator, a polyimide having a high imidization ratio can be obtained at a temperature of 200 ℃.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2018/037997

Non-patent document

Non-patent document 1: M.Uedaetal.chem.Lett, 33(9), p.1156-1157, 2004

Disclosure of Invention

Problems to be solved by the invention

However, the applicant has conducted studies and, as a result, it is not said that the imidization ratio of a cured film obtained by firing the composition described in patent document 1at 200 ℃ is sufficient. Further, it has been found that when a method using a strong acid or a strong base described in non-patent document 1 as an imidization accelerator is applied to a photosensitive resin composition, there are problems that the added imidization accelerator causes decomposition of a photosensitive compound and that the solvent drying step (prebaking) of the photosensitive resin composition for forming a photosensitive resin film causes imidization by heating, thereby deteriorating the pattern processability. Therefore, a material is required which does not cause imidization in the prebaking and which is satisfactorily imidized in the baking step of the photosensitive resin film after the patterning.

Further, the demand for higher reliability of organic EL display devices has been increasing year by year, and materials for planarization layers and materials for insulating layers are required to maintain high film properties even after reliability tests under accelerated conditions such as high temperature, high humidity, and light irradiation, and to obtain characteristics comparable to those obtained when firing is performed at a low temperature.

Accordingly, an object of the present invention is to provide a photosensitive resin composition which has a good imidization rate even when fired at a temperature of 200 ℃ or lower, has high pattern processability, and has high long-term reliability when a cured film is used in an organic EL display device.

Means for solving the problems

In order to solve the above problems, the photosensitive resin composition of the present invention contains a polyimide precursor (a) having a residue derived from a diamine having an ionization potential of less than 7.1eV, a phenol compound (b) having an electron-withdrawing group, and a photosensitive compound (c).

ADVANTAGEOUS EFFECTS OF INVENTION

The photosensitive resin composition of the present invention has a good imidization rate even when fired at a temperature of 200 ℃ or lower, has high pattern processability, and has high long-term reliability when a cured film is used in an organic EL display device.

Drawings

Fig. 1 is a diagram showing a reaction scheme of a dissociation reaction of an acid (proton).

Fig. 2 is a cross-sectional view of an example of a TFT substrate.

Fig. 3 is an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having a bump.

Fig. 4 is a schematic view showing an example of a method for manufacturing a semiconductor device having bumps.

Fig. 5 is a schematic view of a manufacturing process of an organic EL display device in an example.

Detailed Description

The embodiments of the present invention will be described in detail.

The photosensitive resin composition of the present invention contains a polyimide precursor (a) having a residue derived from a diamine having an ionization potential of less than 7.1eV, a phenol compound (b) having an electron-withdrawing group, and a photosensitive compound (c).

< polyimide precursor (a) >)

The photosensitive resin composition of the present invention contains a polyimide precursor (a). The polyimide precursor (a) has a residue derived from a diamine having an ionization potential of less than 7.1 eV. By containing the polyimide precursor (a) and the later-described phenol compound (b) having an electron-withdrawing group, a cured film having a high imidization rate can be obtained even when the cured film is fired at a temperature of 200 ℃ or lower. Further, the long-term reliability can be improved when the cured film of the present invention described later is used as a planarizing layer and/or an insulating layer of an organic EL display device. The polyimide precursor is a resin that is converted into polyimide by heat treatment or chemical treatment. Examples of the polyimide precursor include polyamic acids and polyamic acid esters.

In the present invention, the polyimide precursor preferably has an alkali solubility. The alkali-soluble property in the present invention means that a solution obtained by dissolving the polyimide precursor (a) in γ -butyrolactone is applied to a silicon wafer, prebaked at 120 ℃ for 4 minutes to form a prebaked film having a thickness of 10 μm ± 0.5 μm, the prebaked film is immersed in a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23 ± 1 ℃ for 1 minute, and then rinsed with pure water, and the dissolution rate determined from the decrease in film thickness at that time is 50 nm/minute or more.

In order to impart alkali solubility, the polyimide precursor (a) in the present invention preferably has a hydroxyl group and/or an acidic group in the structural unit of the polyimide precursor (a) and/or at the end of the main chain thereof. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group.

The polyimide precursor (a) preferably has a fluorine atom. By having fluorine atoms, hydrophobicity can be imparted to the cured film.

The polyimide precursor (a) in the present invention preferably has a structural unit represented by the following general formula (3).

In the general formula (3), X represents a 4-7 valent organic group, and Y represents a 2-11 valent organic group. R¹¹And R¹³Each independently represents a hydroxyl group or a sulfonic acid group, and each may be a single group or different groups may be present in combination. R¹²And R¹⁴Each independently represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms. t and w each independently represent an integer of 0 to 3, and v represents an integer of 0 to 6.

The polyimide precursor (a) preferably has 5 to 100000 structural units represented by the general formula (3). The polyimide precursor (a) may have other structural units in addition to the structural unit represented by the general formula (3). In this case, the polyimide precursor (a) preferably has 50 mol% or more of the structural units represented by the general formula (3) among all the structural units.

In the above general formula (3), X (R)¹¹)_t(COOR¹²)₂Denotes the residue of an acid. X is a 4-7 valent organic group, and among them, an organic group having 5-40 carbon atoms containing an aromatic ring or cyclic aliphatic group is preferable.

Examples of the acid include pyromellitic acid, 3,3 ', 4, 4' -biphenyltetracarboxylic acid, 2,3,3 ', 4' -biphenyltetracarboxylic acid, 2 ', 3, 3' -biphenyltetracarboxylic acid, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid, 2 ', 3, 3' -benzophenonetetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane, 1-bis (3, 4-dicarboxyphenyl) ethane, 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-naphthalenetetracarboxylic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 2,3,5, 6-pyridinetetracarboxylic acid, 3,4,9, 10-perylenetetracarboxylic acid, aromatic tetracarboxylic acids having the following structures, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and tetracarboxylic acids such as cyclic aliphatic group-containing aliphatic tetracarboxylic acids such as 1,2,3, 4-cyclopentanetetracarboxylic acid. More than 2 kinds of them may be used.

R²⁰Represents an oxygen atom, C (CF)₃)₂Or C (CH)₃)₂。R²¹And R²²Each independently represents a hydrogen atom or a hydroxyl group.

Among the above acids, in the case of tetracarboxylic acid, 2 carboxyl groups correspond to (COOR) in the general formula (3)¹²)₂。

These acids may be used as they are, or may be used in the form of acid anhydrides, active esters or active amides. Examples of the active ester include an N-hydroxysuccinimide ester compound obtained by reacting an acid carboxyl group with N-hydroxysuccinimide, and examples of the active amide include an N-acylimidazole compound obtained by reacting an acid carboxyl group with N, N' -carbonyldiimidazole.

Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, Examples of the cyclic aliphatic tetracarboxylic acid dianhydride include bis (3, 4-dicarboxyphenyl) ether dianhydride, 1,2,5, 6-naphthalene tetracarboxylic acid dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenic acid dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorenic 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, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, aromatic tetracarboxylic acid dianhydrides such as acid dianhydrides having the structure shown below, aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydrides containing a cyclic aliphatic group such as 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride. More than 2 kinds of them may be used.

R²⁰Represents an oxygen atom, C (CF)₃)₂Or C (CH)₃)₂。R²¹And R²²Each independently represents a hydrogen atom or a hydroxyl group.

Y (R) of the above general formula (3)¹³)_v(COOR¹⁴)_wRepresents the residue of a diamine. Y is a 2-11 valent organic group. The polyimide precursor (a) in the present invention has a residue derived from a diamine having an ionization potential (hereinafter, sometimes referred to as "Ip") of less than 7.1 eV.

In the present invention, the mechanism by which a cured film exhibiting a high imidization rate can be obtained even when fired at a temperature of 200 ℃ or lower is not determined by using the polyimide precursor (a) having a residue derived from a diamine having an ionization potential of less than 7.1eV, but it can be estimated, for example, as follows. That is, the imidization reaction of the polyimide precursor (a) proceeds by nucleophilic attack of the carbonyl carbon of the residue derived from the acid dianhydride by the nitrogen atom of the residue derived from the diamine. The ionization potential is low, i.e., the nucleophilic force of the nitrogen atom of the polyimide precursor having a residue derived from an electron-rich diamine is high. Therefore, it is presumed that the reactivity of the imidization reaction is high and a cured film having a high imidization rate can be obtained even at a temperature of 200 ℃ or lower.

Examples of the diamine having an ionization potential of less than 7.1eV include 2, 7-diaminofluorene (reference value), o-tolidine (reference value), benzidine (reference value, ip 6.73eV), 4 ' -diaminodiphenyl ether (reference value, ip 6.78eV), 1, 4-bis (4-aminophenoxy) benzene (ip 6.80eV), 2-bis [4- (4-aminophenoxy) phenyl ] propane (reference value, ip 6.84eV), 9-bis (4-aminophenyl) fluorene (reference value, ip 6.88eV), 4 ' -diaminodiphenylmethane (ip 6.94eV), p-phenylenediamine (ip 7.03eV), 3 ' -diaminodiphenylmethane (ip 7.08eV), m-tolidine (ip 7.08eV), 1, 3-bis (4-aminophenoxy) benzene (ip 7.08eV), calculated values), etc. More than 2 kinds of them may be used.

The ionization potential is preferably less than 7.0eV, more preferably 6.9eV, and still more preferably 6.8eV, from the viewpoint that a high imidization ratio can be more easily achieved even when the firing is performed at a temperature of 200 ℃ or lower. The lower limit of the ionization potential is not particularly limited, but is about 6.0 eV.

Among them, the residue derived from the diamine having an ionization potential of less than 7.1eV preferably has an ether bond from the viewpoint of improving sensitivity. Among them, the diamine having an ionization potential of less than 7.1eV more preferably contains 1 or more diamines selected from the group consisting of 4, 4' -diaminodiphenyl ether (Ip6.78eV, literature value), 1, 4-bis (4-aminophenoxy) benzene (Ip6.80eV, literature value), 2-bis [4- (4-aminophenoxy) phenyl ] propane (Ip6.84eV, calculated value), and 1, 3-bis (4-aminophenoxy) benzene (Ip7.08eV, calculated value).

In addition, Ip in the present invention is a literature value described in "New edition of latest polyimide" (New latest ポリイミド) (page 102, Anteng Biao treaty). In addition, the values (calculated values) obtained by calculation using Gaussian09 as in the literature values, B3LYP as a general function, and 6-311G (d) (structure optimization calculation) and 6-311+ + G (d, p) (energy calculation) as a basis function were used in the absence of Ip.

The polyimide precursor (a) used in the present invention may contain a diamine residue having an ionization potential of 7.1eV or more in addition to a diamine residue having an ionization potential of less than 7.1eV, in a range in which the above-described characteristics are not degraded. In the case of containing a diamine residue having an ionization potential of 7.1eV or more, the content of a residue derived from a diamine having an ionization potential of less than 7.1eV in 100 mol% of the diamine residues constituting the polyimide precursor (a) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, from the viewpoint of more easily achieving a high imidization rate even when firing is performed at a temperature of 200 ℃. From the viewpoint of further improving the sensitivity, the concentration is preferably 50 mol% or less, and more preferably 40 mol% or less.

Examples of the diamine having an ionization potential of 7.1eV or more include 3,3 ' -diaminodiphenyl ether (ip7.12ev, literature value), 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (ip7.15ev, calculated value), 1, 3-bis (3-aminophenoxy) benzene (ip7.18ev, literature value), 9-bis (3-amino-4-hydroxyphenyl) fluorene (ip7.28ev, calculated value), 3 ' -bis (trifluoromethyl) benzidine (ip7.30ev, literature value), 2-bis (3-amino-4-methylphenyl) hexafluoropropane (ip7.32ev, calculated value), m-phenylenediamine (ip7.39ev, literature value), 2-bis (4-aminophenyl) hexafluoropropane (ip7.41ev, calculated value), 4 ' -diaminodiphenyl sulfone (ip 7.50ev), literature values), 2 ' -bis (trifluoromethyl) benzidine (ip7.55ev, literature values), 3 ' -diaminodiphenyl sulfone (ip7.68ev, literature values), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (ip7.88ev, calculated values), bis (3-amino-4-hydroxyphenyl) sulfone (ip8.02ev, calculated values), aromatic diamines such as compounds in which at least a part of the hydrogen atoms of these aromatic rings is substituted with an alkyl group or a halogen atom, 4 ' -diaminodicyclohexylmethane (ip8.15ev, literature values), aliphatic diamines containing a cyclic aliphatic group such as 1, 4-cyclohexanediamine (ip8.61ev, literature values), diamines containing a silicon atom such as 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (ip8.03ev, calculated values), and diamines (ip 7.16ev) having the structure shown below, calculated values), etc. More than 2 kinds of them may be used.

These diamines may be used as they are, or may be used in the form of, for example, diisocyanate compounds obtained by reacting an amino group of a diamine with phosgene, or in the form of, for example, trimethylsilylated diamines obtained by reacting an amino group of a diamine with chlorotrimethylsilane.

Further, by blocking the ends of these resins with monoamines, acid anhydrides, acid chlorides, monocarboxylic acids, or active ester compounds having an acidic group, a resin having an acidic group at the end of the main chain can be obtained.

Preferable examples of the monoamine having an acidic group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. More than 2 kinds of them may be used.

Preferable examples of the acid anhydride include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexane anhydride, and 3-hydroxyphthalic anhydride. More than 2 kinds of them may be used.

Preferable examples of the monocarboxylic acid include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol and 4-carboxythiophenol. More than 2 kinds of them may be used.

Preferable examples of the acid chloride include a monocarboxylic acid chloride compound obtained by acylating a carboxyl group of the above monocarboxylic acid, and a monocarboxylic acid chloride compound obtained by acylating only 1 carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1, 5-dicarboxylnaphthalene, 1, 6-dicarboxylnaphthalene, 1, 7-dicarboxylnaphthalene, 2, 6-dicarboxylnaphthalene and the like. More than 2 kinds of them may be used.

Preferable examples of the active ester compound include a reaction product of the above-mentioned monoacid chloride compound with N-hydroxybenzotriazole, N-hydroxy-5-norbornene-2, 3-dicarboximide, and the like. More than 2 kinds of them may be used.

The polyimide precursor (a) in the present invention can be synthesized by a known method.

Examples of the method for producing a polyamic acid as a polyimide precursor include a method in which a tetracarboxylic dianhydride and a diamine compound are reacted in a solvent at a low temperature.

Similarly, as a method for producing a polyamic acid ester as a polyimide precursor, in addition to the above-described method for reacting a polyamic acid with an esterifying agent, there can be mentioned: a method of obtaining a diester by reacting a tetracarboxylic dianhydride with an alcohol and then reacting the diester with an amine in a solvent in the presence of a condensing agent; a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is subjected to acid chlorination to react with an amine in a solvent, and the like. From the viewpoint of ease of synthesis, it is preferable to include a step of reacting the polyamic acid with an esterifying agent. The esterification agent is not particularly limited, and a known method can be applied, but N, N-dimethylformamide dialkyl acetal is preferable because purification of the obtained resin is easy.

The polymerization solvent is not particularly limited, and examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate and isobutyl acetate, ketones such as methyl isobutyl ketone and methyl propyl ketone, alcohols such as butanol and isobutanol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, gamma butyrolactone, N-methyl-2-pyrrolidone, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, propylene glycol monomethyl ether acetate, N-dimethylacrylamide, N-isobutyric acid amide, and the like, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-2-imidazolidinone, N-dimethylpropyleneurea, delta valerolactone, 2-phenoxyethanol, 2-pyrrolidone, 2-methyl-1, 3-propanediol, diethylene glycol butyl ether, triethylene glycolAcetin, butyl benzoate, cyclohexylbenzene, bicyclohexane, o-nitroanisole, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, N- (2-hydroxyethyl) -2-pyrrolidone, N, N-dimethylpropane amide, N, N-dimethylisobutyl amide, N, N, N ', N' -tetramethylurea, 3-methyl-2-Oxazolidinones, and the like.

< phenol compound (b) having an electron-withdrawing group >

The photosensitive resin composition of the present invention contains a phenol compound (b) having an electron-withdrawing group (hereinafter, may be simply referred to as "phenol compound (b)"). By containing the polyimide precursor (a) and the phenol compound (b), a cured film having a high imidization rate can be obtained even when the cured film is fired at a temperature of 200 ℃ or lower, and the long-term reliability of the cured film of the present invention, which will be described later, when used as a planarization layer and/or an insulating layer of an organic EL display device can be further improved.

The electron-withdrawing group is a Hammett substituent constant σ defined in revised 5 th edition of handbook of chemistry (list th edition 30990, 5 th edition of chejust), II-379 to II-380 (edited by the society of chemistry of Japan, published by Takayaku corporation)_p ⁰Substituents that are positive values. The phenol compound (b) having an electron-withdrawing group has an electron-withdrawing group in the molecule, so that the acidity of the phenolic hydroxyl group is increased, and the phenol compound (b) functions as an acid catalyst to promote imidization of the polyimide precursor (a).

Specific examples of the electron-withdrawing group include a sulfonyl group, a sulfonic acid group, a sulfonate amide group, a sulfonate imide group, a carboxyl group, a carbonyl group, a carboxylate group, a cyano group, a halogen group, a trifluoromethyl group, a nitro group, and the like. Among them, from the viewpoint of further promoting imidization of the polyimide precursor (a), a carbonyl group, a trifluoromethyl group, a halogen group, and a sulfonyl group are preferable, and a trifluoromethyl group and a sulfonyl group are particularly preferable.

As a preferred form of the phenol compound (b), the phenol compound (b) preferably contains a compound (b1) having a phenolic hydroxyl group with an acid dissociation constant (pKa) of 11.0 or less, which is determined by quantum chemistry calculations based on a density functional method. The compound having a phenolic hydroxyl group with a pKa of 11.0 or less (b1) has a higher acidity of the phenolic hydroxyl group than the acidity of the unsubstituted phenol (pKa of 12.2) obtained by the calculation. On the other hand, since the acidity is not as high as that of a sulfonic acid compound (pKa < 0) known as an imidization accelerator, imidization is not accelerated in a solvent drying step (prebaking) of a photosensitive resin composition described later, and an effect of accelerating imidization in a baking step of a photosensitive resin film after patterning can be improved. The lower limit of the pKa is not particularly limited, but is about 1.0.

The acid dissociation constant (pKa) is the logarithm of the reciprocal of the acid dissociation constant, and in the case of multi-stage dissociation, the dissociation constant of the 1 st stage (i.e., pKa1) is used. As the acid dissociation constant (pKa) in the present invention, an acid dissociation constant calculated by quantum chemical calculation based on a density functional method (DFT method) is used. In such quantum chemical calculations, values obtained by calculation using an electronic computer, Gaussian09, B3LYP as a general function, and 6-311G (d) (structure optimization calculation) and 6-311+ + G (d, p) (energy calculation and vibration analysis) as a basis function are used. In addition, in such quantum chemical calculations, thermodynamic calculations are performed as shown in the reaction scheme of the acid dissociation reaction (dissociation reaction of proton) of the acid (acid represented by formula: HA) shown in FIG. 1. In FIG. 1, HA represents an acid, A^-Denotes the ion of an acid, H⁺Represents a hydrogen ion (proton). In fig. 1, the formula: HA (aq) → H⁺(aq)+A^-(aq) represents the dissociation reaction of protons in water, formula: HA (g) → H⁺(g)+A^-(g) Indicating dissociation reactions of protons in the gas phase.

First, using Gaussian09, Gibbs free energy G in the gas phase of HA was determined⁰ _gas(HA) after the above, the Gibbs free energy difference Δ G between the gas phase and water of HA was calculated by SMD solvation model^＊ _solv(HA). In addition, in the SMD solvation model, the molecular cavity was designated RADII ═ UAHF. Similarly, calculate A^-Of (2)Gibbs free energy G in phase⁰ _gas(A^-) Then, calculate A^-Is the difference in Gibbs free energy Δ G between the gas phase and water^＊ _solv(A^-). Next, using the obtained values, pKa was calculated based on the mathematical formulae (1) to (4). In addition to this calculation, H⁺Gibbs free energy G of⁰ _gas(H⁺) Set to-6.275 kcal/mol, H⁺Is the difference in Gibbs free energy Δ G between the gas phase and water^＊ _solv(H⁺) The value is-1112.5 kJ/mol, the gas constant (R) is 8.314J/(K · mol) ═ 0.0821atm · L/(K · mol), and the absolute temperature (T) is 298.15K.

Specific examples of the compound having a phenolic hydroxyl group with a pKa of 11.0 or less (b1) include bisphenol S (pKa 9.8), bisphenol AF (pKa 10.8), 4- (trifluoromethyl) phenol (pKa 10.5), and the like.

As another preferred form of the phenol compound (b), the phenol compound (b) preferably contains a compound (b2) represented by the general formula (1).

In the general formula (1), A represents a 2-valent group selected from the structures represented by the general formula (2), and a and b each independently represent a whole of 0 to 3A + b is an integer of 2 to 4. In the general formula (2), R¹And R²Each independently represents a halogen atom or a 1-valent organic group having 1 to 20 carbon atoms substituted with a halogen atom.

Since the compound (b2) represented by the general formula (1) has high heat resistance and 2 or more phenolic hydroxyl groups, the effect of improving the long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device can be further improved.

Specific examples of the compound represented by the general formula (1) include bisphenol S (pKa 9.8), bisphenol AF (pKa 10.8), 4' -dihydroxybenzophenone (pKa 11.3), and the like.

The content of the phenol compound (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more, per 100 parts by mass of the polyimide precursor (a). By setting the content in such a range, a high imidization ratio can be easily achieved even when firing is performed at a temperature of 200 ℃. The content of the phenol compound (b) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less. By setting the ratio within such a range, the reduction in the residual film ratio after the alkali development can be easily suppressed.

< photosensitive Compound (c) >)

The photosensitive resin composition of the present invention contains a photosensitive compound (c). Examples of the photosensitive compound (c) include a photoacid generator (c1) and a photopolymerization initiator (c 2). The photoacid generator (c1) is a compound that generates an acid by irradiation with light, and the photopolymerization initiator (c2) is a compound that generates a radical by bond cleavage and/or reaction by exposure.

By containing the photoacid generator (c1), an acid is generated in the light irradiation portion, and the solubility of the light irradiation portion in an alkaline aqueous solution increases, whereby a positive relief pattern in which the light irradiation portion dissolves can be obtained. Further, by containing the photoacid generator (c1) and the epoxy compound or the thermal crosslinking agent described later, the acid generated in the light irradiation section accelerates the crosslinking reaction of the epoxy compound and the thermal crosslinking agent, and a negative relief pattern in which the light irradiation section is not dissolved can be obtained. On the other hand, by containing the photopolymerization initiator (c2) and a radical polymerizable compound described later, radical polymerization proceeds in the light irradiation part, and a negative relief pattern in which the light irradiation part is not dissolved can be obtained.

Examples of the photoacid generator (c1) include quinone diazo compounds, sulfonium salts, and phosphonium salts,Salt, diazoSalt and iodineSalts and the like. The photosensitive resin composition preferably contains 2 or more kinds of photoacid generators, and when the photoacid generator contains 2 or more kinds, a higher sensitivity can be obtained. From the viewpoint of long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device, a quinone diazo compound is particularly preferable as the photoacid generator (c 1).

Examples of the quinone diazo compound include a compound in which a quinone diazo sulfonic acid is bonded to a polyhydroxy compound via an ester, a compound in which a quinone diazo sulfonic acid is bonded to a polyamino compound via a sulfonamide, and a compound in which a quinone diazo sulfonic acid is bonded to a polyhydroxy polyamino compound via an ester and/or a sulfonamide. Preferably, at least 50 mol% of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with a quinone diazide sulfonic acid.

As the quinone diazo structure, any of 5-naphthoquinone diazosulfonyl group and 4-naphthoquinone diazosulfonyl group is preferably used. May contain a naphthoquinone diazosulfonyl ester compound having a 4-naphthoquinone diazosulfonyl group and a 5-naphthoquinone diazosulfonyl group in the same molecule, or may contain a 4-naphthoquinone diazosulfonyl ester compound and a 5-naphthoquinone diazosulfonyl ester compound. The 4-naphthoquinone diazosulfonyl ester compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The 5-naphthoquinone diazosulfonyl ester compound absorbs g-rays extending to the area of the mercury lamp, suitable for g-ray exposure.

The 4-naphthoquinone diazosulfonyl ester compound and the 5-naphthoquinone diazosulfonyl ester compound are preferably selected according to the wavelength of exposure, and the 4-naphthoquinone diazosulfonyl ester compound is preferably contained from the viewpoint of high sensitivity. On the other hand, from the viewpoint of long-term reliability when the cured film of the present invention described later is used as a planarizing layer and/or an insulating layer of an organic EL display device, a 5-naphthoquinone diazosulfonyl ester compound is preferable. However, in the present invention, since the long-term reliability can be improved by containing the polyimide precursor (a) and the phenol compound (b), the 4-naphthoquinone diazosulfonyl ester compound can be suitably used.

The quinone diazide compound can be synthesized from a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound by an arbitrary esterification reaction. By using these quinone diazo compounds, the resolution, sensitivity, and residual film ratio are further improved.

In the present invention, among the photoacid generator (c1), sulfonium salt,Salt, diazoSalt and iodineThe salt is preferable because it moderately stabilizes an acid component generated by exposure. Among them, sulfonium salts are preferable. Further, a sensitizer or the like may be contained as necessary.

In the present invention, in the case of using the photoacid generator (c1), the content thereof is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 25 parts by mass or more, per 100 parts by mass of the polyimide precursor (a), from the viewpoint of high sensitivity. From the viewpoint of further improving the chemical resistance of the cured film, it is preferably 100 parts by mass or less. The content of the photoacid generator (c1) is preferably small from the viewpoint of improving the long-term reliability when the cured film of the present invention described later is used as a planarizing layer and/or an insulating layer of an organic EL display device, but in the present invention, the long-term reliability can be improved by containing the polyimide precursor (a) and the phenol compound (b), and therefore the content of the photoacid generator (c1) can be increased for higher sensitivity.

Examples of the photopolymerization initiator (c2) include benzil ketal photopolymerization initiator, α -hydroxyketone photopolymerization initiator, α -aminoketone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, oxime ester photopolymerization initiator, acridine photopolymerization initiator, titanocene photopolymerization initiator, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, aromatic ketone ester photopolymerization initiator, and benzoate photopolymerization initiator. It may contain 2 or more kinds of photopolymerization initiators (c 2). From the viewpoint of further improving the sensitivity, an α -aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or an oxime ester photopolymerization initiator is more preferable.

Examples of the α -aminoketone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one, and 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-octyl-9H-carbazole.

Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) phosphine oxide, and the like.

Examples of the oxime ester type photopolymerization initiator include 1-phenylpropane-1, 2-dione-2- (O-ethoxycarbonyl) oxime, 1-phenylbutane-1, 2-dione-2- (O-methoxycarbonyl) oxime, 1, 3-diphenylpropane-1, 2, 3-trione-2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl ] octane-1, 2-dione-2- (O-benzoyl) oxime, 1- [4- [4- (carboxyphenyl) thio ] phenyl ] propane-1, 2-dione-2- (O-acetyl) oxime, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- An alkyl ] ethanone-1- (O-acetyl) oxime, 1- [ 9-ethyl-6- [ 2-methyl-4- [1- (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyloxy ] benzoyl ] -9H-carbazol-3-yl ] ethanone-1- (O-acetyl) oxime, or 1- (9-ethyl-6-nitro-9H-carbazol-3-yl) -1- [ 2-methyl-4- (1-methoxypropan-2-yloxy) phenyl ] methanone-1- (O-acetyl) oxime, and the like.

In the present invention, in the case of using the photopolymerization initiator (c2), the content thereof is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 10 parts by mass or more, based on 100 parts by mass of the total of the polyimide precursor (a) and the radical polymerizable compound described later, from the viewpoint of increasing sensitivity. On the other hand, from the viewpoint of further improving the resolution and reducing the taper angle, it is preferably 50 parts by mass or less. In view of improving long-term reliability when the cured film of the present invention described later is used as a planarizing layer and/or an insulating layer of an organic EL display device, the content of the photopolymerization initiator (c2) is preferably small, but in the present invention, since long-term reliability can be improved by containing the polyimide precursor (a) and the phenol compound (b), the content of the photopolymerization initiator (c2) can be increased for higher sensitivity.

< colorant (d) >)

The photosensitive resin composition of the present invention preferably further contains a colorant (d). By containing the colorant (d), light shielding properties for shielding light of a wavelength absorbed by the colorant (d) from light transmitted through or reflected from the film of the photosensitive resin composition can be provided. By providing the light-shielding property, deterioration, malfunction, leakage current, and the like due to light entering the TFT when the cured film of the present invention is used as a planarization layer and/or an insulating layer of an organic EL display device, which will be described later, can be prevented. Further, reflection of external light from the wiring or the TFT is suppressed, and the contrast between the light-emitting region and the non-light-emitting region can be improved.

As the colorant (d), a dye (d1) and/or a pigment (d2) is preferably used. The colorant (d) may contain at least 1 species, and examples thereof include a method using 1 species of dye or organic pigment, a method using 2 or more species of dye or pigment in combination, and a method using 1 or more species of dye and 1 or more species of pigment in combination.

In the present invention, a substance having an absorption maximum value of 400 to 750nm is preferably selected.

From the viewpoint of solvent solubility, the colorant (d) in the present invention is preferably a dye (d 1). On the other hand, the pigment (d2) is preferable from the viewpoint of suppressing the discoloration of the colorant in the step of heat curing the photosensitive resin composition or the photosensitive resin sheet of the present invention described later. However, in the present invention, since the polyimide precursor (a) and the phenol compound (b) are contained, the curing can be performed at a temperature of 200 ℃ or lower, and thus the discoloration of the colorant in the heat curing step can be suppressed even when the dye (d1) is used. Therefore, the dye (d1) can also be suitably used.

In the photosensitive resin composition of the present invention, the colorant (d) preferably contains a dye (d1-1) and/or a pigment (d2-1) having an absorption maximum value in the range of (d-1) wavelength of 400nm or more and less than 490 nm. Hereinafter, they may be abbreviated as component (d-1), component (d1-1) and component (d2-1), respectively.

In the present invention, the dye (d1-1) used as the component (d-1) is preferably a dye which is soluble in an organic solvent in which the polyimide precursor (a) is dissolved and compatible with a resin, or a dye having high heat resistance and light resistance, from the viewpoint of storage stability, curing, and fading upon light irradiation. The component (d1-1) has an absorption maximum value in a wavelength range of 400nm or more and less than 490nm, and examples thereof include yellow dyes and orange dyes. Examples of the type of the dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, direct dyes, and the like.

Examples of the skeleton structure of the dye include anthraquinone-based, azo-based, phthalocyanine-based, methine-based, and azo-based dyes,Oxazine series, quinoline series, triarylmethane series,Ton-based systems, but not limited thereto. Among them, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and the like are preferable from the viewpoint of solubility in organic solvents and heat resistance,And (4) ton series. Furthermore, these dyes may be used alone or in the form of a metal-containing complex salt system. Specifically, substances having an absorption at a wavelength of 400nm or more and a maximum absorption at a wavelength of 490nm or less can be obtained from Sumilan, Lanyl dyes (manufactured by Sumitomo chemical industry Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dyes (チバ. スペシャリティ. ケミカルズ Co., Ltd.), Zapon, Neozapon, Neptune, Acidol dyes (manufactured by BASF Co., Ltd.), Kayaset, Kayakalan dyes (manufactured by Nippon Chemicals Co., Ltd.), Valifast Colors dyes (manufactured by オリエント chemical industry Co., Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dyes (manufactured by クラリアントジャパン Co., Ltd.), Aizen Spilon dyes (manufactured by Sakong chemical industry Co., Ltd.), pigment dyes (manufactured by Shantian chemical industry Co., Ltd.), Plast or dyes, OColil dyes (manufactured by Sumiton chemical industry Co., Ltd.), and the like, but are not limited thereto. These dyes are used alone or by mixing.

In the present invention, the pigment (d2-1) used as the component (d-1) is preferably a pigment having high heat resistance and light resistance, from the viewpoint of discoloration during curing or light irradiation.

Specific examples of the organic pigments used in these are represented by Color Index (CI) numbers. Examples of the yellow pigment include pigment yellow 83, 117, 129, 138, 139, 150, 180, and the like. Examples of orange pigments include pigment orange 38, 43, 64, 71, and 72. In addition, pigments other than these may also be used.

In the case of use in the present invention, the content of the component (d-1) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, relative to 100 parts by mass of the polyimide precursor (a). When the content of the component (d-1) is 0.1 parts by mass or more, light having a wavelength corresponding thereto can be absorbed. Further, when the amount is 300 parts by mass or less, light having a wavelength corresponding to the heat resistance and mechanical properties of the film after heat treatment can be absorbed while maintaining the adhesion strength between the photosensitive colored resin film and the substrate.

In the present invention, as the organic pigment used as the component (d2-1), a surface-treated component such as rosin treatment, acid group treatment, or alkali group treatment may be used, if necessary. Further, it may be used together with a dispersant as the case may be. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants.

The colorant (d) used in the photosensitive resin composition of the present invention preferably contains (d-2) a dye (d1-2) and/or a pigment (d2-2) having an absorption maximum in a wavelength range of 490nm or more and less than 580 nm. Hereinafter, they may be abbreviated as component (d-2), component (d1-2) or component (d 2-2).

In the present invention, the dye used as the component (d1-2) is preferably a dye that is soluble in an organic solvent in which the polyimide precursor (a) is dissolved and compatible with a resin, or a dye having high heat resistance and light resistance, from the viewpoint of storage stability, curing, and fading upon light irradiation. The component (d1-2) has an absorption maximum value in a wavelength range of 490nm or more and less than 580nm, and examples thereof include a red dye and a violet dye. Examples of the type of the dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, direct dyes, and the like.

Examples of the skeleton structure of the dye include anthraquinone-based, azo-based, phthalocyanine-based, methine-based, and azo-based dyes,Oxazine series, quinoline series, triarylmethane series,Ton-based systems, but not limited thereto. Among them, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and the like are preferable from the viewpoint of solubility in organic solvents and heat resistance,And (4) ton series. Furthermore, these dyes may be used alone or in the form of a metal-containing complex salt systemThe preparation is used. Specifically, substances having an absorption value in a wavelength range of 490nm or more and 580nm or less can be obtained from Sumilan, Lanyl dyes (manufactured by Sumitomo chemical industries, Ltd.), Orasol, Oracet, Filamid, Irgasperse dyes (manufactured by チバ, スペシャリティ, ケミカルズ, Ltd.), Zapon, Neozapon, Neptune, Acidol dyes (manufactured by BASF, Ltd.), Kayaset, Kayakalan dyes (manufactured by Nippon Chemicals, Ltd.), Valifast Colors dyes (manufactured by オリエント, chemical engineering , Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dyes (manufactured by クラリアントジャパン, Ltd.), Aizen Spilon dyes (manufactured by Baoka chemical industries, Ltd.), functional pigments (manufactured by Shantian chemical industries, Ltd.), Plast or dyes, OColor dyes (manufactured by Sulo chemical industries, Ltd.), and the like, but not limited thereto. These dyes are used alone or by mixing.

In the present invention, the pigment (d2-2) used as the component (d-2) is preferably a pigment having high heat resistance and light resistance, from the viewpoint of discoloration during curing or light irradiation.

Specific examples of the organic pigments used in these are represented by Color Index (CI) numbers. Examples of red pigments include pigment red 48: 1. 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc. Examples of the violet pigment include pigment violet 19, 23, 29, 32, 33, 36, 37, and 38. In addition, pigments other than these may also be used.

In the case of use in the present invention, the content of the component (d-2) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, relative to 100 parts by mass of the polyimide precursor (a). When the content of the component (d-2) is 0.1 parts by mass or more, light having a wavelength corresponding thereto can be absorbed. Further, when the amount is 300 parts by mass or less, light having a wavelength corresponding to the heat resistance and mechanical properties of the film after heat treatment can be absorbed while maintaining the adhesion strength between the photosensitive colored resin film and the substrate.

In the present invention, as the organic pigment used as the component (d2-2), one having a surface treated with rosin treatment, acid group treatment, alkali group treatment or the like as required can be used. Further, it may be used together with a dispersant as the case may be. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants.

The colorant (d) used in the photosensitive resin composition of the present invention preferably contains (d-3) a dye (d1-3) and/or a pigment (d2-3) having an absorption maximum value in a wavelength range of 580nm or more and less than 800 nm.

In the present invention, the dye (d1-3) used as the component (d-3) is preferably a dye which is soluble in an organic solvent in which the polyimide precursor (a) is dissolved and compatible with a resin, or a dye having high heat resistance and light resistance, from the viewpoint of storage stability, curing, and fading upon light irradiation. The component (d1-3) has an absorption maximum value in a wavelength range of 580nm or more and less than 800nm, and examples thereof include a blue dye and a green dye.

Examples of the type of the dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, direct dyes, and the like.

Examples of the skeleton structure of the dye include anthraquinone-based, azo-based, phthalocyanine-based, methine-based, and azo-based dyes,Oxazine series, quinoline series, triarylmethane series,Ton-based systems, but not limited thereto. Among them, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and the like are preferable from the viewpoint of solubility in organic solvents and heat resistance,And (4) ton series. In addition, these dyes can be used alone or as metal complex salt system and use. Specifically, they can be selected from Sumilan, Lanyl dyes (manufactured by Sumitomo chemical industries, Ltd.), Orasol, Oracet, Filamid, Irgasperse dyes (manufactured by チバ, スペシャリティ, ケミカルズ), Zapon, Neozapon, and Cyanopsis,Neptune, Acidol dye (BASF), Kayaset, Kayakalan dye (Japan chemical products), Valifast Colors dye (オリエント chemical ), Savinyl, Sandoplast, Polysynthren, Lanasyn dye (クラリアントジャパン), Aizen Spilon dye (Baotu chemical industries), functional pigments (Shantian chemical industries), plat Color dye, Oil Color dye (local chemical industries), etc., but the present invention is not limited thereto. These dyes may be used alone or by mixing.

In the present invention, the pigment (d2-3) used as the component (d-3) is preferably a pigment having high heat resistance and light resistance, from the viewpoint of discoloration during curing or light irradiation.

Specific examples of the organic pigments used in these are represented by Color Index (CI) numbers. Examples of the blue pigment include pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like. Examples of the green pigment include pigment green 7, 10, 36, 47, 58, and the like. In addition, pigments other than these may also be used.

In the present invention, the content of the component (d-3) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, relative to 100 parts by mass of the polyimide precursor (a). When the content of the component (d-3) is 0.1 parts by mass or more, light having a wavelength corresponding thereto can be absorbed. Further, when the amount is 300 parts by mass or less, light having a wavelength corresponding to the heat resistance and mechanical properties of the film after heat treatment can be absorbed while maintaining the adhesion strength between the photosensitive colored resin film and the substrate.

In the present invention, as the organic pigment used as the component (d2-3), a surface-treated one such as a rosin treatment, an acid group treatment, or a basic group treatment may be used, if necessary. Further, it may be used together with a dispersant as the case may be. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants.

In the present invention, the component (d-1), the component (d-2) and the component (d-3) are used in combination to make the black color. The blackening can be expressed by optical density (OD value), and the OD value is preferably 0.3 or more, more preferably 0.6 or more, and further preferably 1.0 or more.

< thermochromatic Compound >

The photosensitive resin composition of the present invention may further contain a thermochromatic compound. The thermochromatic compound is a thermochromatic compound which develops color by heat treatment and has an absorption maximum value of 350nm to 700nm, and more preferably a thermochromatic compound which develops color by heat treatment and has an absorption maximum value of 350nm to 500 nm. By using a thermochromatic compound in place of the component (d-1) or in combination with the component (d-1), the absorption of the photosensitive resin composition in the exposure wavelength region of 350-450nm can be suppressed, and the decrease in sensitivity can be suppressed.

In the present invention, the thermochromatic compound is preferably a compound which develops color at a temperature higher than 120 ℃, and more preferably a thermochromatic compound which develops color at a temperature higher than 180 ℃. The thermochromatic compound has excellent heat resistance under high temperature conditions as the color temperature thereof is higher, and is less discolored by irradiation with ultraviolet light and visible light for a long time, and is excellent in light resistance.

In the present invention, the thermochromatic compound may be a general thermal dye or pressure sensitive dye, or may be another compound. Examples of the thermochromatic compound include a substance that develops color by changing its chemical structure or charge state by the action of an acidic group coexisting in the system during heat treatment, a substance that develops color by a thermal oxidation reaction or the like in the presence of oxygen in the air, and the like.

Examples of the skeleton structure of the thermochromatic compound include triarylmethane skeleton, diarylmethane skeleton, fluoran skeleton, dilactone skeleton, phthalide skeleton, and the like,Xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenothiazine skeleton, and thiopheneAn oxazine skeleton, a spiropyran skeleton, and the like. Among them, a triarylmethane skeleton is preferable because of its high thermal color development temperature and excellent heat resistance.

Specific examples of the triarylmethane skeleton include 2,4 ' -methylene trisphenol, 4 ' - [ (4-hydroxyphenyl) methylene ] bis (aniline), 4 ' - [ (4-aminophenyl) methylene ] bisphenol, 4 ' - [ (4-aminophenyl) methylene ] bis [3, 5-dimethylphenol ], 4 ' - [ (2-hydroxyphenyl) methylene ] bis [2,3, 6-trimethylphenol ], 4- [ bis (4-hydroxyphenyl) methyl ] -2-methoxyphenol, 4 ' - [ (2-hydroxyphenyl) methylene ] bis [ 2-methylphenol ], 4 ' - [ (4-hydroxyphenyl) methylene ] bis [ 2-methylphenol ], and the like, 4- [ bis (4-hydroxyphenyl) methyl ] -2-ethoxyphenol, 4 '- [ (4-hydroxyphenyl) methylene ] bis [2, 6-dimethylphenol ], 2' - [ (4-hydroxyphenyl) methylene ] bis [3, 5-dimethylphenol ], 4 '- [ (4-hydroxy-3-methoxyphenyl) methylene ] bis [2, 6-dimethylphenol ], 2' - [ (2-hydroxyphenyl) methylene ] bis [2,3, 5-trimethylphenol ], 4 '- [ (4-hydroxyphenyl) methylene ] bis [2,3, 6-trimethylphenol ], 4' - [ (2-hydroxyphenyl) methylene ] bis [ 2-cyclohexyl-5-methylphenol ], 4,4 '- [ (4-hydroxyphenyl) methylene ] bis [ 2-cyclohexyl-5-methylphenol ], 4' - [ (3-methoxy-4-hydroxyphenyl) methylene ] bis [ 2-cyclohexyl-5-methylphenol ], 4 '- [ (3, 4-dihydroxyphenyl) methylene ] bis [2, 6-dimethylphenol ], 4' - [ (3, 4-dihydroxyphenyl) methylene ] bis [2,3, 6-trimethylphenol ], and the like. They may be used alone or in admixture thereof. In addition, as for the hydroxyl group-containing compound having a triarylmethane skeleton, a sulfonic acid of naphthoquinone diazide may be ester-bonded to the compound, and the compound may be used as a quinone diazide compound.

In the present invention, the content of the thermochromatic compound is preferably 5 to 80 parts by mass, and particularly preferably 10 to 60 parts by mass, based on 100 parts by mass of the polyimide precursor (a). When the content of the thermochromatic compound is 5 parts by mass or more, the transmittance in the ultraviolet-visible light region of the cured film can be reduced. Further, when the amount is 80 parts by mass or less, the heat resistance and strength of the cured film can be maintained, and the water absorption rate can be reduced.

< resin other than polyimide precursor (a) >)

The photosensitive resin composition of the present invention may contain a resin other than the polyimide precursor (a). Examples of the resin (a) other than the polyimide precursor (a) include polyimide and polybenzeneExamples of the polymerizable monomer include, but are not limited to, an azole precursor, polyamideimide precursor, polyamide, a polymer of a radical polymerizable monomer having an acidic group, and a phenol resin. These resins preferably have alkali solubility, and 2 or more of these resins may be contained. Among these resins, polyimide and polybenzene are more preferable from the viewpoint of high long-term reliability when a cured film to be described later is used in an organic EL display device due to high adhesion by development, excellent heat resistance, and a small amount of gas release at high temperatureAzole precursors or copolymers thereof. Here, the term "polybenzo" is usedAn azole precursor refers to a precursor which is converted into a polybenzazole by heat treatment or chemical treatmentExamples of the resin of azole include polyhydroxyamide.

< radical polymerizable Compound >

The photosensitive resin composition of the present invention may further contain a radical polymerizable compound.

The radical polymerizable compound is a compound having a plurality of ethylenically unsaturated double bonds in the molecule. In the exposure, radical polymerization of the radical polymerizable compound is performed by radicals generated from the photopolymerization initiator (c2), and the irradiated portion is insolubilized, thereby obtaining a negative pattern. By further containing a radical polymerizable compound, photocuring of the light irradiation section is promoted, and the sensitivity is further improved. Further, since the crosslinking density after heat curing is increased, the hardness of the cured film can be increased.

The radical polymerizable compound is preferably a compound having a (meth) acryloyl group, which is easily subjected to radical polymerization. From the viewpoint of improving sensitivity at the time of exposure and improving hardness of the cured film, a compound having two or more (meth) acryloyl groups in a molecule is more preferable. The double bond equivalent of the radical polymerizable compound is preferably 80 to 400g/mol from the viewpoint of improving sensitivity during exposure and improving hardness of the cured film.

Examples of the radical polymerizable compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, 2-bis [4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl ] propane, 1,3, 5-tris ((meth) acryloyloxyethyl) isocyanurate, 1, 3-bis ((meth) acryloyloxyethyl) isocyanurate, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, and mixtures thereof, 9, 9-bis [4- (3- (meth) acryloyloxypropoxy) phenyl ] fluorene, 9-bis (4- (meth) acryloyloxyphenyl) fluorene, or an acid-modified form thereof, an ethylene oxide-modified form thereof, a propylene oxide-modified form thereof, and the like.

In the photosensitive resin composition of the present invention, the content of the radical polymerizable compound is preferably 15 parts by mass or more, and more preferably 30 parts by mass or more, based on 100 parts by mass of the total of the polyimide precursor (a) and the radical polymerizable compound, from the viewpoint of further improving the sensitivity and reducing the cone angle. On the other hand, from the viewpoint of further improving the heat resistance of the cured film and reducing the taper angle, it is preferably 65 parts by mass or less, more preferably 50 parts by mass or less.

< thermal crosslinking agent >

The photosensitive resin composition of the present invention may further contain a thermal crosslinking agent. The thermal crosslinking agent is a compound having at least 2 thermally reactive functional groups such as an alkoxymethyl group, a hydroxymethyl group, an epoxy group, and an oxetanyl group in the molecule. By containing a thermal crosslinking agent, the polyimide precursor (a) or other additive components can be crosslinked, and the heat resistance, chemical resistance, and folding resistance of the film after heat curing can be improved. On the other hand, from the viewpoint of improving the imidization rate during low-temperature firing and improving the long-term reliability when the cured film of the present invention described later is used as a planarizing layer and/or an insulating layer of an organic EL display device, a thermal crosslinking agent containing no epoxy group or oxetane group is preferable. This is presumably because, when the photosensitive resin composition of the present invention contains a thermal crosslinking agent such as an epoxy group and an oxetane group which react with a phenolic hydroxyl group, the phenolic hydroxyl group of the phenolic compound (b) reacts with the thermal crosslinking agent, and the effect of the present invention is reduced.

Preferred examples of the compound having at least 2 alkoxymethyl groups or hydroxymethyl groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DML-MBPC, TriML-P, TriML-35XL, TML-BPA HQ, TML-PP-BPF, TML-BPE, TML-BPA, TML-BPAP, TML-BPBP, TMOM-BPE, TMBPOM-BPOM-AP, TMBPOM-BPOM-BPAP, TMBPOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by NIKALAC, Inc.), "NIKALAC" (registered trade name), MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (trade name, manufactured by LTD., LTD.), and ケミカル.

Preferred examples of the compound having at least 2 epoxy groups include "エポライト" (registered trademark) 40E, "エポライト" 100E, "エポライト" 200E, "エポライト" 400E, "エポライト" 70P, "エポライト" 200P, "エポライト" 400P, "エポライト" 1500NP, "エポライト" 80MF, "エポライト" 4000, "エポライト" 3002 (see above, manufactured by Kyoeisha chemical Co., Ltd.), "デナコール" (registered trademark) EX-212L, "デナコール" EX-214L, "デナコール" EX-216L, "デナコール" EX-850L (see above, manufactured by ナガセケムテックス (Co., Ltd.)), GAN, GOT (see above, manufactured by Nippon chemical Co., Ltd.), "エピコート" (registered trademark) 828, and, "エピコート" 1002, "エピコート" 1750, "エピコート" 1007, "YX 8100-BH30, E1256, E4250, E4275 (see above, ジャパンエポキシレジン (manufactured by LTD.)," エピクロン "(registered trademark) EXA-9583, HP4032 (see above, DIC (manufactured by LTD.), VG3101 (manufactured by Mitsui Chemicals (Co., Ltd.))), "テピック" (registered trademark) S, "テピック" G, "テピック" P (manufactured by Nissan chemical industry Co., Ltd.), "デナコール" EX-321L (manufactured by ナガセケムテックス Co., Ltd.), NC6000 (manufactured by Nippon chemical Co., Ltd.), "エポトート" (registered trademark) YH-434L (manufactured by Tokyo chemical industry Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon chemical Co., Ltd.), "エピクロン" (registered trademark) N695, HP7200 (manufactured by DIC Co., Ltd.), and the like.

Preferred examples of the compound having at least 2 oxetanyl groups include エタナコール EHO, エタナコール OXBP, エタナコール OXTP, エタナコール OXMA (manufactured by Utsu corporation), oxetanated phenol novolak, and the like.

The thermal crosslinking agent may contain 2 or more species in combination.

When the thermal crosslinking agent is contained, the content thereof is preferably 1 mass% or more and 30 mass% or less with respect to 100 mass% of the total amount of the photosensitive resin composition excluding the solvent. If the content of the thermal crosslinking agent is 1 part by mass or more, the chemical resistance and the bending resistance of the cured film can be further improved. Further, if the content of the thermal crosslinking agent is 30 parts by mass or less, the amount of outgas from the cured film can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the photosensitive resin composition is also excellent.

< solvent >

The photosensitive resin composition of the present invention may further contain a solvent. By containing a solvent, a varnish state can be formed, and the coatability can be improved.

Examples of the solvent include polar aprotic solvents such as γ -butyrolactone, 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 diethylene glycol monomethyl etherEthers such as alkanes, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 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, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl n-propylhomobenzoate, n-butylpiperazinoate, and mixtures thereof, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate and other esters, toluene, xyleneAromatic hydrocarbons such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, amides such as 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-dimethylpropanamide and N, N-dimethylisobutylamide, 3-methyl-2-Oxazolidinones, and the like. May contain 2 or more of them.

When the solvent is contained, the content is not particularly limited, but is preferably 100 to 3000 parts by mass, and more preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. The proportion of the solvent having a boiling point of 180 ℃ or higher is preferably 20% by mass or lower, and more preferably 10% by mass or lower, out of 100% by mass of the total amount of the solvent. By setting the proportion of the solvent having a boiling point of 180 ℃ or higher to 20 mass% or lower, the amount of outgas after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

Sealing modifier

The photosensitive resin composition of the present invention may further contain an adhesion improving agent. Examples of the adhesion improving agent include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. May contain 2 or more of them. By containing these adhesion improving agents, the adhesion improving agents can be improved in the adhesion to a silicon wafer, Indium Tin Oxide (ITO), SiO, etc. when a resin film is developed₂And development adhesion of a base substrate such as silicon nitride. Further, resistance to oxygen plasma and UV ozone treatment used for washing and the like can be improved. When the adhesion improver is contained, the adhesion improver is added to a solvent other than the solventThe content of the photosensitive resin composition is preferably 0.01 to 10% by mass based on 100% by mass of the total amount of the photosensitive resin composition.

< surfactant >

The photosensitive resin composition of the present invention may further contain a surfactant as necessary, and the wettability with the substrate can be improved. Examples of the surfactant include, for example, examples of the surfactant include SH series, SD series, ST series, BYK series of ビックケミー - ジャパン series of Chinese gall stone レ - ダウコーニング (strain), KP series of shin-Etsu chemical industry (strain), ディスフォーム series of Japanese oil (strain), メガファック (registered trademark) series of DIC (strain), フロラード series of Sumitomo スリーエム (strain), サーフロン (registered trademark) series of Asahi Nitri (strain), "アサヒガード (registered trademark)" series, ポリフォックス series of オムノヴァ - ソルーション (strain), acrylic and/or methacrylic surfactants such as ポリフロー series of Kyoeisha chemical (strain), ディスパロン (registered trademark) series of Naguchi chemical (strain), and the like.

When the surfactant is contained, the content is preferably 0.001 to 1% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the solvent.

< inorganic particles >

The photosensitive resin composition of the present invention may further contain inorganic particles. Preferable specific examples of the inorganic particles include, for example, silica, titanium oxide, barium titanate, alumina, talc, and the like. The primary particle diameter of the inorganic particles is preferably 100nm or less, more preferably 60nm or less.

When the inorganic particles are contained, the content is preferably 5 to 90% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the solvent.

< method for producing photosensitive resin composition >

Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition of the present invention can be obtained by dissolving the polyimide precursor (a), the phenol compound (b), the photosensitive compound (c), and, if necessary, the colorant (d), the thermochromatic compound, the radical polymerizable compound, the thermal crosslinking agent, the solvent, the adhesion improver, the surfactant, the inorganic particles, and the like.

Examples of the dissolving method include stirring and heating. When heating is performed, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually from room temperature to 80 ℃. The order of dissolving the components is not particularly limited, and examples thereof include a method of dissolving the components in order from a compound having low solubility. Further, with respect to components which tend to generate bubbles when dissolved by stirring, such as the surfactant and a part of the adhesion improver, by dissolving other components and then adding them at last, it is possible to prevent the dissolution failure of other components due to the generation of bubbles.

The obtained photosensitive resin composition is preferably filtered by a filter to remove dust and particles. Examples of the pore diameter of the filter include, but are not limited to, 0.5. mu.m, 0.2. mu.m, 0.1. mu.m, 0.07. mu.m, 0.05. mu.m, and 0.02. mu.m. Examples of the material of the filter include polypropylene (PP), Polyethylene (PE), Nylon (NY), Polytetrafluoroethylene (PTFE), and the like. Among them, polyethylene and nylon are preferable.

< photosensitive resin film, photosensitive resin sheet >

The photosensitive resin sheet of the present invention is a photosensitive resin sheet formed from the photosensitive resin composition of the present invention. The photosensitive resin sheet of the present invention can be obtained by, for example, applying and drying the photosensitive resin composition of the present invention to a releasable substrate such as polyethylene terephthalate.

In the present invention, the photosensitive resin film can be obtained by coating the photosensitive resin composition of the present invention to obtain a coating film of the photosensitive resin composition, and drying the coating film. Further, the photosensitive resin sheet may be made into a photosensitive resin film.

Examples of the method for applying the photosensitive resin composition of the present invention include spin coating, slit coating, dip coating, spray coating, and printing. Among them, the slit coating method is preferable because coating can be performed with a small amount of coating liquid and cost reduction is facilitated. The amount of the coating liquid required for the slit coating method is about 1/5 to 1/10, for example, as compared with the spin coating method. As the slit nozzle used for coating, for example, a slit nozzle marketed by a plurality of manufacturers such as "リニアコーター" manufactured by japan スクリーン corporation, "スピンレス" manufactured by tokyo chemical industry corporation, "TS コーター" manufactured by imperial レエンジニアリング corporation, "テーブルコータ" manufactured by china and foreign furnace industry corporation, "CS series" and "CL series" manufactured by tokyo エレクトロン corporation, "インライン type ス リ ッ ト コーター" manufactured by サーマトロニクス easy corporation, and "ヘ ッ ド コーター HC series" manufactured by platane engineur corporation may be selected. The coating speed is generally in the range of 10 mm/sec to 400 mm/sec. The thickness of the coating film varies depending on the solid content concentration, viscosity, etc. of the resin composition, but the coating film is usually applied so that the film thickness after drying becomes 0.1 to 10 μm, preferably 0.3 to5 μm.

Before coating, the substrate to which the photosensitive resin composition is applied may be pretreated with the adhesion improving agent in advance. Examples of the pretreatment method include a method in which the surface of the substrate is treated with a solution obtained by dissolving 0.5 to 20 mass% of the adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of the method for treating the surface of the base material include spin coating, slit die coating, bar coating, dip coating, spray coating, and vapor treatment.

After coating, a reduced pressure drying treatment is performed as necessary.

The reduced pressure drying rate is related to the volume of the vacuum chamber, the capacity of the vacuum pump, the diameter of the piping between the chamber and the pump, and the like, but for example, in a state where the substrate is not coated, it is preferable to set a condition that the pressure in the vacuum chamber is reduced to 40Pa after 60 seconds. The reduced-pressure drying time is generally about 30 seconds to 100 seconds, and the pressure reached in the vacuum chamber after the reduced-pressure drying is usually 100Pa or less in a state where the coated substrate is present. By setting the reaching pressure to 100Pa or less, a dried state in which the stickiness of the surface of the coating film is reduced can be formed, and thereby the surface contamination and the generation of particles during the subsequent substrate transfer can be suppressed.

After coating or drying under reduced pressure, the coating film is generally dried by heating. This process is also referred to as pre-baking. The drying is performed by using an electric heating plate, an oven, infrared rays, or the like. In the case of using an electric hot plate, the coating film is held directly on the plate and heated, or held on a jig such as a contact pin provided on the plate and heated. The heating time is preferably 1 minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but is preferably 80 ℃ or higher, and more preferably 90 ℃ or higher, from the viewpoint of promoting the drying of the solvent at the time of prebaking. On the other hand, from the viewpoint of reducing the progress of imidization at the prebaking, it is preferably 150 ℃ or lower, and more preferably 140 ℃ or lower. The photosensitive resin composition of the present invention contains the polyimide precursor (a) and the phenol compound (b) to suppress the progress of imidization during prebaking, but can obtain a cured film having a high imidization rate even when fired at a temperature of 200 ℃.

The photosensitive resin film and the photosensitive resin sheet may form a pattern. For example, a desired pattern can be formed by irradiating a photosensitive resin film and a photosensitive resin sheet with a chemical ray through a mask having a desired pattern, exposing the film to light, and developing the film.

Examples of the chemical radiation used for the exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-ray (365nm), h-ray (405nm), and g-ray (436nm) of a mercury lamp are preferably used. In the case of having positive photosensitivity, the exposed portion is dissolved in a developer. In the case of having negative photosensitivity, the exposed portion is cured and does not dissolve in the developer.

After exposure, the exposed portion is removed by a developer in the case of a positive type, and the unexposed portion is removed by a developer in the case of a negative type, thereby forming a desired pattern. The developer is preferably an aqueous solution of a compound exhibiting basicity, such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and 1, 6-hexamethylenediamine. To these alkaline aqueous solutions, 1 or more kinds of polar solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, γ -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 may be added. Examples of the development method include a jet method, a paddle method, a dipping method, an ultrasonic method, and the like.

Next, the pattern formed by the development is preferably subjected to a rinsing treatment with distilled water. Alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and the like may be added to distilled water to carry out rinsing treatment.

< cured film >

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention. The photosensitive resin composition of the present invention and the photosensitive resin sheet of the present invention are cured by heating, whereby components having low heat resistance can be removed, and thus heat resistance and chemical resistance can be further improved. In particular, since the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention contains a polyimide precursor and forms an imide ring by heat curing, the heat resistance and chemical resistance can be further improved.

The cured film of the present invention can be suitably used for, for example, a planarization layer and/or an insulating layer in an organic EL display device having a driver circuit, a planarization layer, a1 st electrode, an insulating layer, a light-emitting layer, and a 2 nd electrode on a substrate.

The cured film of the present invention can be suitably used for an interlayer insulating layer and/or a surface protective layer in an electronic component having an electrode, a metal wiring, an interlayer insulating layer, and/or a surface protective layer on a substrate, for example.

< method for producing cured film >

A first aspect of the method for producing a cured film of the present invention includes the steps of: forming a photosensitive resin film made of the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention on a substrate; exposing the photosensitive resin film to light; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film at 200 ℃ or lower.

The second aspect of the method for producing a cured film of the present invention includes the steps of: forming a photosensitive resin film made of the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention on a substrate; exposing the photosensitive resin film to light; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film in an atmosphere having an oxygen concentration of 1% or more. In the present invention, the oxygen concentration represents a volume concentration.

The step of forming the photosensitive resin film, the step of exposing the photosensitive resin film, and the step of developing the exposed photosensitive resin film in the method for producing a cured film of the present invention are as described in the above item < photosensitive resin film, photosensitive resin sheet >.

The first aspect of the method for producing a cured film of the present invention includes a step of heat-treating a photosensitive resin film at 200 ℃ or lower. The photosensitive resin composition of the present invention contains the polyimide precursor (a) and the phenol compound (b), and thus can obtain a cured film having a high imidization rate even when heat treatment is performed at 200 ℃. In particular, when the photosensitive resin composition further contains a colorant (d), the heat treatment at 200 ℃ or lower is preferable from the viewpoint of more easily suppressing the discoloration of the colorant (d).

In the method for producing a cured film of the present invention, the temperature in the step of the heat treatment may be raised stepwise or continuously.

In the method for producing a cured film of the present invention, the atmosphere during thermal curing is preferably an inert gas atmosphere from the viewpoint of further reducing the amount of outgas generated from the cured film and improving the long-term reliability when the cured film is used as a planarizing layer and/or an insulating layer of an organic EL display device. Specific examples of the inert gas include nitrogen gas and argon gas.

In the first aspect of the method for producing a cured film of the present invention, the oxygen concentration in the inert gas atmosphere is preferably 5% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.01% or less.

In the first aspect of the method for producing a cured film of the present invention, the heating time in the step of the heat treatment is preferably 30 minutes or more, from the viewpoint of further reducing the amount of outgas. In the present invention, the heating time means a holding time at the maximum reaching temperature in the heat treatment step. In addition, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or less. Examples of the heat treatment include a method of heat-treating at 200 ℃ for 30 minutes, a method of heat-treating at 150 ℃ and 200 ℃ for 30 minutes each, and a method of heat-treating while linearly raising the temperature from room temperature to 200 ℃ over 2 hours.

The second embodiment of the method for producing a cured film of the present invention includes a step of heat-treating the developed photosensitive resin film in an atmosphere having an oxygen concentration of 1% or more. The photosensitive resin composition of the present invention contains the polyimide precursor (a) and the phenol compound (b), and thus can improve long-term reliability when a cured film is used as a planarization layer and/or an insulating layer of an organic EL display device, and therefore can be suitably cured by heating even at an oxygen concentration of 1% or more.

In the second aspect of the method for producing a cured film of the present invention, the temperature in the heat treatment step is preferably 180 ℃ or higher, more preferably 200 ℃ or higher, further preferably 230 ℃ or higher, and particularly preferably 250 ℃ or higher, from the viewpoint of further reducing the amount of outgas generated from the cured film. On the other hand, the temperature is preferably 500 ℃ or lower, more preferably 450 ℃ or lower, from the viewpoint of improving the film toughness of the cured film.

In the second aspect of the method for producing a cured film of the present invention, when the photosensitive resin composition further contains the colorant (d), the temperature in the heat treatment step is preferably 230 ℃ or less, and more preferably 200 ℃ or less, from the viewpoint of easily suppressing the discoloration of the colorant (d).

In the second aspect of the method for producing a cured film of the present invention, the heating time in the step of the heat treatment is preferably 30 minutes or more, from the viewpoint of further reducing the amount of outgas. In addition, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or less. Examples of the heat treatment include a method of heat-treating at 250 ℃ for 30 minutes, a method of heat-treating at 150 ℃ and 250 ℃ for 30 minutes, and a method of heat-treating while linearly raising the temperature from room temperature to 300 ℃ over 2 hours.

< example of application of photosensitive resin composition, photosensitive resin sheet and cured film >

The photosensitive resin composition, the photosensitive resin sheet and the cured Film of the present invention are suitably used for a surface protective layer of a semiconductor element, an interlayer insulating layer, an insulating layer of an organic Electroluminescence (EL) element, a planarization layer of a Thin Film Transistor (TFT) substrate for driving of a display device using an organic EL element, a wiring protective insulating layer of a circuit board, an on-chip microlens of a solid-state imaging element, and a planarization layer for various displays and solid-state imaging elements. For example, a surface protective layer and an interlayer insulating layer are suitable as MRAM having low heat resistance, Polymer Ferroelectric RAM (PFRAM), Phase Change RAM (PCRAM), and other Polymer memories (OUM) which are promising as next-generation memories. The present invention can also be used for an insulating layer of a display device including a first electrode formed on a substrate and a second electrode provided so as to face the first electrode, for example, an LCD, an ECD, an ELD, a display device using an organic electroluminescent element (an organic electroluminescent device), or the like. Hereinafter, an organic EL display device, a semiconductor device, and a semiconductor electronic component will be described as examples.

< organic EL display device >

The organic EL display device of the present invention is an organic EL display device having a driving circuit, a planarizing layer, a1 st electrode, an insulating layer, a light-emitting layer, and a 2 nd electrode on a substrate, and the planarizing layer and/or the insulating layer has the cured film of the present invention. Organic light-emitting materials are generally not resistant to gas components and moisture, and when exposed to these, the emission luminance decreases and pixels shrink. Here, the pixel reduction refers to a phenomenon in which the light emission luminance decreases from the end portion of the pixel or becomes unlit. The organic EL display device of the present invention can improve long-term reliability by including the cured film of the present invention in the planarization layer and/or the insulating layer of the organic EL display device. In particular, since the insulating layer is adjacent to the organic light-emitting material, the influence on the long-term reliability is large as compared with the planarization layer. Therefore, in order to obtain an organic EL display device having high long-term reliability, it is preferable that at least the insulating layer includes the cured film of the present invention.

In an active matrix display device, for example, a substrate made of glass, various plastics, or the like is provided with TFTs and wirings located on side portions of the TFTs and connected to the TFTs, and a planarization layer is provided thereon so as to cover irregularities, and a display element is further provided on the planarization layer. The display element and the wiring are connected via a contact hole formed in the planarization layer. In particular, in recent years, organic EL display devices have become mainstream because flexibility has become dominant, and therefore, an organic EL display device in which a substrate having the driving circuit includes a resin film is preferable. The cured film obtained by curing the photosensitive resin composition or the photosensitive sheet of the present invention is particularly preferably used as an insulating layer or a planarizing layer of such a flexible display because it has excellent bending resistance. Polyimide is particularly preferable as the resin film from the viewpoint of improving adhesion to a cured film obtained by curing the photosensitive resin composition or the photosensitive sheet of the present invention.

The thickness of the cured film of the present invention when used as the planarizing layer is preferably 1.0 to 5.0. mu.m, and more preferably 2.0 μm or more. By setting the planarizing layer within the above range, the flatness of the TFTs and the wirings which are densely packed with high definition can be improved. If the planarizing layer is made thicker, outgassing increases and long-term reliability of the organic EL display device decreases, but the cured film of the present invention can improve long-term reliability even when the film is made thicker. Further, since the TFT and the wiring may be arranged in the film thickness direction for higher definition, the planarization layer is preferably a plurality of layers, and the planarization layer is more preferably 2 to5 layers.

Fig. 2 shows a cross-sectional view of an example of the TFT substrate. Bottom gate type or top gate type TFTs (thin film transistors) 1 are provided in a matrix on the substrate 6, and a TFT insulating layer 3 is formed so as to cover the TFTs 1. Further, a wiring 2 connected to the TFT1 is provided on the TFT insulating layer 3. Further, a planarization layer 4 is provided on the TFT insulating layer 3 in a state where the wiring 2 is embedded. The planarization layer 4 is provided with a contact hole 7 reaching the wiring 2. Further, in a state of being connected to the wiring 2 through the contact hole 7, an ITO (transparent electrode) 5 is formed on the planarizing layer 4. Here, ITO5 serves as an electrode of a display element (e.g., an organic EL element). Further, an insulating layer 8 is formed so as to cover the periphery of the ITO 5. The organic EL element may be of a top emission type in which light is emitted from the side opposite to the substrate 6, or of a bottom emission type in which light is extracted from the substrate 6 side. In this manner, an active matrix organic EL display device in which the TFT1 for driving each organic EL element is connected to each organic EL element is obtained.

Such a TFT insulating layer 3, a planarization layer 4, and/or an insulating layer 8 can be formed by the following steps: a step of forming a photosensitive resin film formed from the photosensitive resin composition or the photosensitive resin sheet of the present invention; exposing the photosensitive resin film to light; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film. By the manufacturing method having these steps, an organic EL display device can be obtained.

< electronic component >

The electronic component of the present invention is an electronic component having an electrode and a metal wiring on a substrate, and further having an interlayer insulating layer and/or a surface protective layer, and at least a part of the interlayer insulating layer and/or the surface protective layer has the cured film of the present invention.

Specific examples of the electronic component include active components having semiconductors such as transistors, diodes, integrated circuits (hereinafter, referred to as ICs), and memories, and passive components such as resistors, capacitors, and inductors. Hereinafter, an electronic component using a semiconductor is sometimes referred to as a semiconductor device.

Specific examples of the cured film in the electronic component include a passivation film of a semiconductor, a surface protective film of a semiconductor element, a TFT, and the like, an interlayer insulating film in a multilayer wiring for high-density mounting of 2 to 10 layers, an insulating film of a touch panel display, a protective film, and the like, but are not limited thereto, and various structures can be adopted.

When a semiconductor device is used as an example, the cured film of the present invention has excellent mechanical properties, and therefore, when it is mounted, stress from the sealing resin can be relaxed, and breakage of the low-k layer can be suppressed, whereby a highly reliable semiconductor device can be provided.

Fig. 3 is an enlarged cross-sectional view showing an example of a pad portion of a semiconductor device having a bump. An Al pad 10 for input/output and a passivation layer 11 having a through hole are formed on the silicon wafer 9. Further, an insulating layer 12 is formed on the passivation layer 11, and further, a metal layer 13 made of Cr, Ti, or the like is formed so as to be connected to the Al pad 10, and a metal wiring 14 made of Al, Cu, or the like is formed by electrolytic plating or the like. The metal layer 13 around the solder bump 18 is etched to insulate the pads from each other. Barrier metal 16 and solder bumps 18 are formed on the insulated pads. When the insulating film 15 is processed, a scribe line 17 is formed.

Next, a method for manufacturing a semiconductor device will be described with reference to the drawings. Fig. 4 shows an example of a method for manufacturing a semiconductor device having bumps. In the step 3a, the photosensitive resin composition of the present invention is applied to the silicon wafer 9 on which the Al pad 10 and the passivation layer 11 are formed, and the insulating layer 12 is formed by patterning through a photolithography step. Next, in the step 3b, the metal layer 13 is formed by sputtering. In the step 3c, the metal wiring 14 is formed on the metal layer 13 by plating. Next, in the step 3 d', the photosensitive resin composition of the present invention is applied, and in the step 3d, the insulating layer 15 is patterned through a photolithography step. At this time, the resin composition constituting the insulating layer 15 is processed into a thick film at the scribe line 17. A wiring (so-called rewiring) may be further formed on the insulating layer 15. When a multilayer wiring structure having 2 or more layers is formed, the above-described steps are repeated, whereby a multilayer wiring structure having 2 or more layers of rewiring separated by an interlayer insulating layer formed of a cured film of the present invention can be formed. There is no upper limit to the number of layers of the multilayer wiring structure, but 10 or less layers are often used. Next, in the step 3e, the barrier metal 16 is formed, and in the step 3f, the solder bump 18 is formed. Further, the semiconductor device having the bump can be obtained by dicing the semiconductor device into individual pieces by dicing along the last scribe line 17.

Examples

The present invention will be described below by way of examples, but the present invention is not limited to these examples. In addition, each evaluation in examples was performed by the following method.

(1) Imidization rate

The varnishes obtained in the examples and comparative examples were applied to a silicon wafer by a spin coating method using a spin coater (MS-A100; ミカサ, Inc.) at an arbitrary rotation speed. Next, a pre-baked film having a film thickness of 2.0 μm was prepared by baking the film at 120 ℃ for 2 minutes using a hot plate (SCW-636; manufactured by Dainippon スクリーン). Further, the film thickness was measured under the condition of a refractive index of 1.63 using ラムダエース STM-602 manufactured by japan スクリーン (japan). The obtained prebaked film was cut into 3 pieces, and the 1 st piece was not subjected to any treatment, and the 2 nd piece was subjected to heat treatment using an inert oven CLH-21CD-S (manufactured by Toyo サーモシステム Co., Ltd.) at 200 ℃ for 1 hour in a nitrogen atmosphere having an oxygen concentration of 0.01%, and the 3 rd piece was subjected to heat treatment at 250 ℃ for 1 hour in a nitrogen atmosphere having an oxygen concentration of 0.01%, to thereby prepare a photosensitive resin composition prebaked film and cured films at 200 ℃ and 250 ℃.

The infrared absorption spectra of the obtained pre-baked film and the cured films at 200 ℃ and 250 ℃ were obtained by the ATR method using a fourier transform infrared spectrophotometer (manufactured by japan spectrophotometer). Based on the formula (5), the cured film obtained after heating at 250 ℃ for 1 hour was designed to have an imidization rate of 100%, and the thickness of the cured film was 1371cm from the thickness of the polyimide C-N-C film of each sample^-1Absorption intensity of (A) (1371 cm)^-1) And 1437cm from benzene ring)^-1Absorption intensity of (A) (1437 cm)^-1) The imidization ratios (%) of the pre-baked film and the cured film at 200 ℃ were calculated, respectively. In the formula (5), X (%) represents the imidization rate. The film was judged to be "A" when the imidization rate of the cured film at 200 ℃ was 90% or more, "B" when the imidization rate was less than 90% and 75% or more, and "C" when the imidization rate was less than 75%. Further, the film was judged to be "C" even when the imidization ratio of the cured film at 200 ℃ was 75% or more and the imidization ratio of the pre-baked film was 30% or more.

(2) Sensitivity (Pattern processability)

The varnishes obtained in the examples and comparative examples were coated on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by kyoto エレクトロン, by imperial and imperial that can, or an imperial imper. Further, the film thickness was measured under the condition of a refractive index of 1.63 using ラムダエース STM-602 manufactured by japan スクリーン (japan). Then, an exposure machine i-ray stepper NSR-2005i9C (manufactured by ニコン) was used to expose an exposure dose of 50 to 300mJ/cm to a pattern having contact holes of 10 μm through a mask having a pattern of contact holes²In the range of every 5mJ/cm²And (6) carrying out exposure. After exposure, a 2.38 mass% tetramethylammonium aqueous solution (hereinafter, TMAH, manufactured by Moore chemical industries, Ltd.) was used as a developer in the developing apparatus of ACT-8, and the film was developed until the film reduction amount became 0.5. mu.m, and then the development was carried out with distilled waterAnd (5) washing, shaking and drying to obtain the pattern.

The obtained pattern was observed at a magnification of 20 times using an FDP microscope MX61(オリンパス, ltd.), and the opening diameter of the contact hole was measured. The lowest exposure dose at which the opening diameter of the contact hole reached 10 μm was obtained and used as the sensitivity. Sensitivity is less than 150mJ/cm²Is judged as "S" when the concentration is 150mJ/cm²Above and less than 200mJ/cm²Is judged as "A" in the case of (1), and is 200mJ/cm²Above and less than 250mJ/cm²Is determined as "B" when the measured value is 250mJ/m²In the above case, it is determined as "C".

(3) Residual film rate

The prebaked film having a thickness of 3.0 μm obtained in the same manner as in the sensitivity evaluation in (2) was developed with a developing apparatus of ACT-8 using a 2.38 mass% TMAH aqueous solution as a developer for 60 seconds, and then rinsed with distilled water and dried by shaking to obtain a developed film. The ratio of the thickness of the developed film to the thickness of the prebaked film was defined as a residual film ratio (thickness of the developed film)/(thickness of the prebaked film) × 100). The film residue rate is determined as "a" when the film residue rate is 80% or more, "B" when the film residue rate is less than 80% and 65% or more, and "C" when the film residue rate is less than 65%.

(4) Evaluation of Long-term reliability of organic EL display device

Fig. 5 shows a schematic diagram of a manufacturing process of the organic EL display device. First, an ITO transparent conductive film was formed on the entire surface of a 38mm × 46mm alkali-free glass substrate 19 by a sputtering method by 10nm, and was etched as a first electrode (transparent electrode) 20. In addition, at the same time, an auxiliary electrode 21 for taking out the second electrode is also formed. The substrate thus obtained was ultrasonically washed with セミコクリーン 56 (trade name, フルウチ chemical corporation) for 10 minutes, and then washed with ultrapure water. Then, the photosensitive resin compositions shown in tables 2 and 3 were applied to the entire surface of the substrate by spin coating, and prebaked on a 120 ℃ hot plate for 2 minutes. After UV exposure of the film through a photomask, the film was developed with a 2.38 mass% TMAH aqueous solution to dissolve unnecessary portions, and the film was rinsed with pure water. The obtained resin pattern was heat-treated at 200 ℃ for 1 hour in a nitrogen atmosphere having an oxygen concentration of 0.01% using an inert oven CLH-21CD-S (manufactured by Toyobo サーモシステム Co., Ltd.). In this manner, openings having a width of 70 μm and a length of 260 μm were arranged at a pitch of 155 μm in the width direction, openings having a width of 70 μm and a length of 260 μm were arranged at a pitch of 465 μm in the length direction, and the respective openings were defined in the substrate effective region to form the insulating layer 22 in a shape in which the first electrode was exposed. This operation formed an insulating layer having an opening ratio of 25% in the effective area of the substrate of a square shape having a side of 16 mm. The thickness of the insulating layer was about 1.0 μm.

Next, after nitrogen plasma treatment as a pretreatment, the organic EL layer 23 including the light-emitting layer was formed by a vacuum evaporation method. The degree of vacuum during vapor deposition was 1X 10^-3Pa or less, the substrate is rotated relative to the deposition source during deposition. First, compound (HT-1) was deposited at 10nm as a hole injection layer, and compound (HT-2) was deposited at 50nm as a hole transport layer. Then, a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40nm so that the dopant concentration became 10%. Next, the compound (ET-1) as an electron transporting material and the compound (LiQ) were laminated at a volume ratio of 1:1 to have a thickness of 40 nm. The structure of the compound used in the organic EL layer is shown below.

Next, after 2nm of the compound (LiQ) was deposited, Mg and Ag were deposited at a volume ratio of 10:1 for 10nm to prepare a second electrode (non-transparent electrode) 24. Finally, the lid-like glass plate was bonded and sealed with an epoxy resin adhesive in a low-humidity nitrogen atmosphere, and 4 rectangular top-emission organic EL display devices each having a side length of 5mm were fabricated on 1 substrate. Here, the film thickness is a value indicated by a crystal oscillation type film thickness monitor.

The organic EL display device thus fabricated was mounted with the light-emitting surface facing upwardIrradiating with electric heating plate heated to 80 deg.C at wavelength of 365nm and illuminance of 0.6mW/cm²UV light of (1). Immediately after the irradiation (0 hour), 250 hours, 500 hours, and 1000 hours later, the organic EL display device was driven by a direct current of 0.625mA to emit light, and the area ratio of the light-emitting portion to the area of the light-emitting pixel (pixel light-emitting area ratio) was measured. The pixel light-emitting area ratio after 1000 hours has elapsed obtained by this evaluation method is determined as "S" when it is 80% or more, "a" when it is less than 80% and 70% or more, "B" when it is less than 70% and 60% or more, and "C" when it is less than 60%.

Synthesis example 1 Synthesis of hydroxyl group-containing diamine Compound (. alpha.)

18.3g (0.05 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100mL of acetone and 17.4g (0.3 mol) of propylene oxide, and the solution was cooled to-15 ℃. A solution of 20.4g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100mL of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction mixture was allowed to react at-15 ℃ for 4 hours and then returned to room temperature. The precipitated white solid was isolated by filtration and dried under vacuum at 50 ℃.

30g of the solid was charged into a 300mL stainless steel autoclave, dispersed in 250mL of methyl cellosolve, and 2g of 5% palladium-carbon was added. In which hydrogen was introduced by balloon and reduction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated and the reaction was terminated. After the completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (α) (ip7.16ev, calculated value) represented by the following formula.

Synthesis example 2 Synthesis of quinone diazo Compound (c-1)

21.22g (0.05 mol) of TrisP-PA (trade name, manufactured by chemical industry, Japan) and 36.27g (0.135 mol) of 5-naphthoquinone diazosulfonyl chloride were dissolved in 1,4-II450g of an alkane was allowed to stand at room temperature. In which 1, 4-bis (tert-butyl) and 1, 4-bis (tert-butyl) are added dropwise in such a manner that the temperature in the system does not become more than 35 DEG C50g of an alkane and 15.18g of mixed triethylamine. After the dropwise addition, the mixture was stirred at 30 ℃ for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration. The precipitate was dried by a vacuum dryer to obtain a quinone diazo compound (c-1) represented by the following formula.

Synthesis example 3 Synthesis of alkali-soluble resin (a-1)

Odpa31.02g (0.10 mole) was dissolved in NMP500g under a stream of dry nitrogen gas. To this, BAHF23.81g (0.065 mol), o-tolidine 4.25g (0.02 mol), and SiDA1.24g (0.005 mol) were added together with NMP50g, and the mixture was reacted at 40 ℃ for 2 hours. Next, MAP2.18g (0.02 mol) as a capping agent was added together with NMP5g, and the mixture was allowed to react at 50 ℃ for 2 hours. Then, 32.39g (0.22 mol) of N, N-dimethylformamide diethylacetal was diluted with NMP50 g. After the addition, the mixture was stirred at 50 ℃ for 3 hours. After completion of stirring, the solution was cooled to room temperature, and then the solution was poured into 3L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried with a vacuum drier at 80 ℃ for 24 hours to obtain a polyimide precursor (a-1).

Synthesis examples 4 to 15 and comparative Synthesis examples 1 to 3

Polyimide precursors (a-2) to (a-13) and (a '-1) to (a' -3) were obtained in the same manner as in synthesis example 3, except that the amine component and the acid component were changed as shown in table 1.

The following structural formulae are shown for the names of the compounds used in the synthesis examples, comparative synthesis examples, examples and comparative examples, HMOM-TPHAP, VG 3101L.

O-tolidine: ortho-tolidine (Ip6.58eV, literature value)

And (3) DAE: 4, 4' -diaminodiphenyl ether (Ip6.78eV, literature value) (diamine with ether bond)

MDA: 4, 4' -diaminodiphenylmethane (Ip6.94eV, literature values)

TDE-R: 1, 3-bis (4-aminophenoxy) benzene (ip7.08ev, calculated) (diamine with ether bond)

BAHF: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Ip7.88eV, calculated)

SiDA: 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (Ip8.03eV, calculated)

MAP: 3-aminophenols

ODPA: 3,3 ', 4, 4' -Diphenyl Ether Tetraformic dianhydride

6 FDA: 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride

b-1: bisphenol AF (pKa 10.8) (phenol compound (b) having an electron-withdrawing group satisfying the requirements of (b1) and (b 2))

b-2: bisphenol S (pKa 9.8) (phenol compound (b) having an electron-withdrawing group satisfying the requirements of (b1) and (b 2))

b-3: 4, 4' -dihydroxybenzophenone (pKa 11.3) (phenol compound (b) having an electron-withdrawing group satisfying the requirement of (b 2))

b-4: 4- (trifluoromethyl) phenol (pKa 10.5) (phenol compound (b) having an electron-withdrawing group satisfying the requirement of (b 1))

b-5: 3- (trifluoromethyl) phenol (pKa 11.2) (phenol compound (b) having an electron-withdrawing group)

b' -1: bisphenol a (pKa ═ 11.6) (phenol compound having no electron-withdrawing group)

b' -2: p-cresol (pKa ═ 12.8) (phenol compound having no electron-withdrawing group)

GBL: gamma-butyrolactone

NMP: n-methyl pyrrolidone

TsOH: p-toluenesulfonic acid

DBU: 1, 8-diazabicyclo [5.4.0] -7-undecene

Example 1

A varnish of a positive photosensitive resin composition was obtained by adding 10.0g of the polyimide precursor (a-1), 2.0g of the phenol compound (b-1), and 2.0g of the quinone diazo compound (c-1) to GBL30 g. The resulting varnish was used to evaluate the imidization ratio, sensitivity, residual film ratio, and long-term reliability of the organic EL display device as described above.

Examples 2 to 23, comparative examples 1 to 7, and comparative examples 10 to 15

Varnish of a positive photosensitive resin composition was obtained in the same manner as in example 1, except that the polyimide precursor (a), the phenol compound (b), the photosensitive compound (c), and other additives were changed as described in table 2. The resulting varnish was used to evaluate the imidization ratio, sensitivity, residual film ratio, and long-term reliability of the organic EL display device as described above.

Example 24

The long-term reliability of the organic EL display device was evaluated in the same manner as in example 2, except that the varnish obtained in example 2 was used and the heat treatment temperature of the resin pattern was changed from 200 ℃ to 250 ℃.

Example 25

The long-term reliability of the organic EL display device was evaluated in the same manner as in example 2, except that the varnish obtained in example 2 was used and the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 1%.

Example 26

The long-term reliability of the organic EL display device was evaluated in the same manner as in example 2, except that the varnish obtained in example 2 was used and the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 5%.

Example 27

The long-term reliability of the organic EL display device was evaluated in the same manner as in example 2, except that the varnish obtained in example 2 was used and the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to an atmospheric atmosphere having an oxygen concentration of 21%.

Example 28

A varnish of a positive type photosensitive resin composition was obtained by adding 10.0g of the polyimide precursor (a-2), 2.0g of the phenol compound (b-1), 2.0g of the quinone diazo compound (c-1), 2.5g of 4, 4' -methylene trisphenol (e-1), 1.5g of Valifast Red 1308(d1-2-1), and 2.5g of Oil Blue613(d1-3-1) to GBL30 g. The resulting varnish was used to evaluate the imidization ratio, sensitivity, residual film ratio, and long-term reliability of the organic EL display device as described above. The heat treatment atmosphere of the resin pattern was an atmospheric atmosphere having an oxygen concentration of 21%, and the heat treatment temperature was set to 200 ℃.

Then, a cured film having a thickness of 1.0 μm and heat-treated at 200 ℃ was formed on the alkali-free glass substrate in the same manner as in the imidization ratio (1). The incident light intensity (I0) and transmitted light intensity (I) of the cured film thus produced were measured by a transmission densitometer (X-Rite361T (V); manufactured by X-Rite Co., Ltd.). As an index of light-shielding property, the OD value was calculated by the following formula and was 0.6.

OD value log₁₀(I0/I)。

Example 29

The long-term reliability of the organic EL display device was evaluated in the same manner as in example 28, except that the varnish obtained in example 28 was used and the heat treatment temperature of the resin pattern was changed from 200 ℃ to 250 ℃.

Then, the OD value of the cured film was calculated in the same manner as in example 28 except that the heat treatment temperature was changed from 200 ℃ to 250 ℃, and as a result, the coloring agent partially faded during the heat treatment, and the OD value was 0.3.

Comparative example 8

10.0g of the polyimide precursor (a' -1) and 2.0g of the quinone diazo compound (c-1) were added to GBL30 g. TsOH1.0g was added thereto to obtain a varnish of a positive photosensitive resin composition. The resulting varnish was used to evaluate the imidization ratio, sensitivity, residual film ratio, and long-term reliability of the organic EL display device as described above.

Comparative example 9

10.0g of the polyimide precursor (a' -1) and 2.0g of the quinone diazo compound (c-1) were added to GBL30 g. When DBU1.0g was added thereto, the varnish was blackened, and the decomposition products of the quinone diazo compound were precipitated, whereby the evaluation was suspended.

Comparative example 16

The long-term reliability of the organic EL display device was evaluated in the same manner as in comparative example 1, except that the varnish obtained in comparative example 1 was used and the heat treatment temperature of the resin pattern was changed from 200 ℃ to 250 ℃.

Comparative example 17

The long-term reliability of the organic EL display device was evaluated in the same manner as in comparative example 1, except that the varnish obtained in comparative example 1 was used, and the heat treatment atmosphere of the resin pattern was changed from an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 1%.

Comparative example 18

The long-term reliability of the organic EL display device was evaluated in the same manner as in comparative example 1, except that the varnish obtained in comparative example 1 was used, and the heat treatment atmosphere of the resin pattern was changed from an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 5%.

Comparative example 19

The long-term reliability of the organic EL display device was evaluated in the same manner as in comparative example 1, except that the varnish obtained in comparative example 1 was used, and the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to an atmospheric atmosphere having an oxygen concentration of 21%.

The compositions and evaluation results of the examples and comparative examples are shown in tables 2 to 5.

[ Table 1]

[ Table 2-1]

[ TABLE 2-1]

[ tables 2-2]

[ TABLE 2-2]

[ Table 3]

[ TABLE 3]

[ Table 4-1]

[ tables 4-2]

[ Table 5-1]

[ tables 5-2]

Description of the reference numerals

1: TFT (thin film transistor)

2: wiring

3: TFT insulating layer

4: planarization layer

5: ITO (transparent electrode)

6: substrate

7: contact hole

8: insulating layer

9: silicon wafer

10: al gasket

11: passivation layer

12: insulating layer

13: metal (Cr, Ti, etc.) layer

14: metal wiring (Al, Cu, etc.)

15: insulating layer

16: barrier metal

17: score line

18: solder bump

19: alkali-free glass substrate

20: first electrode (transparent electrode)

21: auxiliary electrode

22: insulating layer

23: organic EL layer

24: a second electrode (non-transparent electrode).