JP2021155467A - Resin, photosensitive resin composition, cured material, organic el display device, semiconductor device and manufacturing method of cured material - Google Patents

Abstract

To provide a method of overcoming a difficulty of combining flatness, fine pattern processabilty and pattern dimension stability which is caused by difficulty of imparting the photosensitivity, as the photosensitive resin composition, due to a silsesquioxane structure in the resin and a problem of insufficient compatibility with the photosensitive agent, a crosslinking agent, a dissolution accelerator or the like, turbidity of a coated film, development unevenness or the development residue.SOLUTION: One or more kinds of resins (A) selected from the group consisting of polyimides, polybenzoxazoles, polyimide precursors, polybenzoxazole precursors and copolymers of two or more kinds thereof, and the resin (A) is a resin (A) having a silsesquioxane structure and the resin (A) having a weak acid group having an acid dissociation constant of 13.0 or larger and 23.0 or smaller in the main chain and/or terminal of the resin (A).SELECTED DRAWING: None

Description

The present invention relates to resins. Specifically, a surface protective film or interlayer insulating film of a semiconductor device, an insulating film of an organic electroluminescence (hereinafter referred to as EL) display device, and a flattening film of a thin film transistor (hereinafter referred to as TFT) substrate for driving. The present invention relates to resins suitable for applications such as wiring protective insulating films for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening films for various displays and solid-state imaging devices.

Since heat-resistant resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, they are used as surface protective films, interlayer insulating films, insulating layers for organic EL display devices, and display devices for semiconductor devices such as LSIs. It is used as a flattening film for TFT substrates.
In recent years, in organic EL display devices and semiconductor devices, the density of pixels and wiring has been increasing, and there is a demand for a material suitable for fine processing of patterns and flattening of an object surface having an uneven surface.
As an example of the high flattening material, a polyimide resin in which a cage-type silsesquioxane structure is introduced into the main chain has been proposed (see, for example, Patent Documents 1 and 2). Further, there is an example in which a resin having a cage-type silsesquioxane structure is used as an insulating film or a protective film of an electric solid device such as a semiconductor device (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2004-331647 Japanese Unexamined Patent Publication No. 2006-53807 JP-A-2007-302635

However, the techniques of Patent Documents 1 to 3 have a silsesquioxane structure having low reactivity in the resin, so that it is difficult to impart photosensitivity as a photosensitive resin composition, and flattening property is also satisfied. It was difficult to achieve both fine pattern processability and pattern dimensional stability. Further, the compatibility with the photosensitizer, the cross-linking agent, the dissolution accelerator and the like is insufficient, and there are problems that the coating film becomes cloudy, development unevenness and development residue are generated.

In order to solve the above problems, the resin (A) of the present invention has the following constitution.
One or more kinds of resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and two or more kinds of copolymers thereof, and in the structure of the resin (A). It has a silsesquioxane structure, and the acid dissociation constant (hereinafter, also referred to as pKa) in dimethylsulfoxide (hereinafter, also referred to as DMSO) is determined at the main chain and / or the terminal of the resin (A). Resin (A) having a weakly acidic group of 0 or more and 23.0 or less.

INDUSTRIAL APPLICABILITY The present invention has good compatibility with a photosensitizer, a cross-linking agent, a dissolution accelerator, etc., can impart photosensitivity as a photosensitive resin composition, and has flattening property for filling irregularities and flattening. Provided is a resin having both fine pattern processability and pattern dimensional stability.

Cross-sectional view of flatness evaluation sample

Embodiments of the present invention will be described in detail.

The resin (A) of the present invention is one or more kinds of resins (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and two or more kinds of copolymers thereof. , The resin (A) has a silsesquioxane structure, and a weakly acidic group having a pKa in DMSO of 13.0 or more and 23.0 or less is attached to the main chain and / or the terminal of the resin (A). It is a resin (A) having.

<Resin (A)>
The polyimide and the polyimide precursor can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride or the like with a diamine, a corresponding diisocyanate compound, a trimethylsilylated diamine or the like, and tetra. It has a carboxylic acid residue and a diamine residue. For example, a polyimide can be obtained by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic acid dianhydride with diamine, by heat treatment. During this heat treatment, a solvent that azeotropes with water, such as m-xylene, can also be added. Alternatively, a dehydration condensing agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a ring-closing catalyst such as a base such as triethylamine can be added to dehydrate and ring-close the ring by chemical heat treatment. Alternatively, a weakly acidic carboxylic acid compound can be added to dehydrate and ring closure by heat treatment at a low temperature of 100 ° C. or lower.

Polybenzoxazole and polybenzoxazole precursors can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, etc., and a dicarboxylic acid residue and a bisaminophenol residue can be obtained. Have. For example, polybenzoxazole can be obtained by dehydrating and closing the ring of polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, by heat treatment. Alternatively, anhydrous phosphoric acid, a base, a carbodiimide compound, or the like can be added to dehydrate and close the ring by chemical treatment.
Further, the reaction time and the reaction temperature can be adjusted in the process of dehydration ring closure, or for example, after the polyimide is polymerized, the polyamic acid or the polybenzoxazole precursor can be continuously polymerized to obtain a copolymer. The copolymer may be a block copolymer or a random copolymer.

<Silsesquioxane structure>
The resin (A) has a silsesquioxane structure. By having the silsesquioxane structure, an appropriate reflow property is exhibited in the resin, and a resin having excellent flatness of unevenness can be obtained. Silsesquioxane is a synonym for a compound in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms. In the present invention, silsesquioxane is a synonym. The structure also includes a compound having a silsesquioxane-like structure in which a part thereof is modified. Examples of the silsesquioxane structure include a ladder structure, a completely condensed type structure, an incompletely condensed type structure, and an amorphous structure that does not show a constant structure.
The structural units of siloxane are shown in the general formulas (1-1) to (1-4).

In the general formulas (1-1) to (1-4), R ¹ represents an organic group having 1 or more carbon atoms and 100 or less carbon atoms, which is bonded to a hydrogen atom, a halogen atom, or silicon with a carbon atom.

The resin (A) contains silsesquioki represented by the general formula (1-3) with respect to a total of 100 mol% of all siloxane constituent units represented by the general formulas (1-1) to (1-4). The content of the sun constituent unit is preferably 50 mol% or more, more preferably 70 mol% or more. By containing the structural unit represented by the general formula (1-3) in the above ratio, it becomes easy to develop an appropriate reflow property of the silsesquioxane structure, and both flatness and pattern dimensional stability are compatible. It will be easier to remove.
Further, from the viewpoint of compatibility, flattening property, and pattern dimensional stability, it is preferable to have a silsesquioxane structure in the main chain of the resin (A).

The silsesquioxane structure in the resin (A) preferably contains a cage-type silsesquioxane structure from the viewpoint of compatibility, flattening property, and pattern dimensional stability. The cage-type silsesquioxane structure may include an incompletely condensed type structure in addition to the completely condensed type structure. The completely condensed structure is a structure composed of a plurality of cyclic structures and forming a closed space, and the shape of the closed space is not limited. The incompletely condensed type structure is a structure in which at least one or more parts of the completely condensed type structure are not closed and the space is not closed.

The silsesquioxane structure in the resin (A) can be easily detected by the following method. The resin (A) can be directly detected by a pyrolysis gas chromatograph (PGC), an infrared spectrum, a 29Si-NMR spectrum, a 13C-NMR spectrum, and a 1H-NMR spectrum measurement. Separately, the resin (A) is dissolved in an acidic or basic solution, decomposed into an amine component and an acid component, which are constituent units of the resin (A), and this is decomposed into gas chromatography (GC) or NMR measurement. By doing so, the silsesquioxane structure can be easily detected.

In order to obtain the resin (A) having a silsesquioxane structure, for example, a silsesquioxane structure-containing polyvalent acid anhydride, a silsesquioxane structure-containing polyvalent carboxylic acid chloride, and a silsesquioxane structure-containing polyvalent acid are obtained. One or more monomers selected from the group consisting of valent carboxylic acid active esters and silsesquioxane structure-containing polyvalent amines are used. Silcesquioxane structure-containing polyvalent acid anhydrides, silsesquioxane structure-containing polyvalent carboxylic acid chlorides, silsesquioxane structure-containing polyvalent carboxylic acid active esters, and silsesquioxane structure-containing polyvalent amines are particularly important. There are no restrictions, and commercially available products and those obtained by conventionally known manufacturing methods can also be used. (See, for example, JP-A-2004-331647, JP-A-2006-265243, JP-A-2007-302635, JP-A-2005-232024, and JP-A-2010-538114.)
Examples of the silsesquioxane-containing acid anhydride include acid anhydrides having a structure represented by the general formulas (3-1) to (3-10).

In the general formulas (3-1) to (3-10), R is an organic group having 1 or more carbon atoms and 100 or less carbon atoms bonded to a hydrogen atom, a halogen atom, or a silicon atom by a carbon atom, respectively. Q is independently a hydrogen atom, a halogen atom, or an organic group having 1 or more and 100 or less carbon atoms. Y is a group represented by the general formula (3-Y). The structures of R, Q, and Y may be different from each other.

In the general formula (3-Y), Y ¹ is an organic group having 2 or more carbon atoms and 100 or less carbon atoms, and * is bonded to a silicon atom.

In the general formulas (3-1) to (3-10), R is not particularly limited, but is alkyl having 1 to 40 carbon atoms, cycloalkyl having 4 to 10 carbon atoms, and any hydrogen is halogen or 1 to 1 carbon atoms. Aryl which may be replaced by an alkyl of 20 or an arylalkyl composed of an aryl in which any hydrogen may be replaced by a halogen or an alkyl having 1 to 20 carbon atoms and an alkylene having 1 to 8 carbon atoms. The group selected by Any hydrogen atom may be replaced by a fluorine atom, and any −CH ₂ − may be replaced by −O −, −CH ₂ = CH ₂ −, or −CH ₃ ≡ _{CH 3 −.} More specifically, a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a trifluoromethyl group, a hexafluoroisopropyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a vinyl group and an allyl group. , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

In the general formulas (3-1) to (3-10), Q is not particularly limited, but is an alkyl having 1 to 40 carbon atoms, a cycloalkyl having 4 to 10 carbon atoms, and any hydrogen is halogen or 1 to 1 carbon atoms. Independent of aryls that may be replaced by an alkyl of 20 and arylalkyls composed of aryls in which any hydrogen may be replaced by halogens or alkyls having 1 to 20 carbons and alkylenes having 1 to 8 carbons. Is the group that is selected. Any hydrogen atom may be replaced by a fluorine atom, and any −CH ₂ − may be replaced by −O −, −CH ₂ = CH ₂ −, or −CH ₃ ≡ _{CH 3 −.} More specifically, a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a trifluoromethyl group, a hexafluoroisopropyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a vinyl group and an allyl group. , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

In the general formulas (3-1) to (3-10), Y specifically includes, but is not limited to, a structure represented by the following structural formula.

The silsesquioxane structure-containing polyvalent acid anhydride is preferably a polyvalent acid anhydride having a structure represented by the general formulas (3-1) to (3-5) from the viewpoint of easiness of polymerization. ..
The resin (A) preferably contains a cage-type silsesquioxane structure from the viewpoint of compatibility, flattening property, and pattern dimensional stability. That is, it is more preferable to use a polyvalent acid anhydride having a structure represented by the general formula (3-1) and the general formula (3-2) as a raw material. Further, it is preferable to have a cage-type silsesquioxane structure in the main chain of the resin (A). That is, it is more preferable to use a polyhydric acid anhydride having a structure represented by the general formula (3-1) as a raw material.

Examples of the silsesquioxane-containing multivalent amine include polyvalent amines having structures represented by the general formulas (4-1) to (4-10).

In the general formulas (4-1) to (4-10), R is an organic group having 1 or more carbon atoms and 100 or less carbon atoms bonded to a hydrogen atom, a halogen atom, or a silicon atom by a carbon atom, respectively. Q is independently a hydrogen atom, a halogen atom, or an organic group having 1 or more and 100 or less carbon atoms. Z is an organic group having an amino group and having 1 or more carbon atoms and 100 or less carbon atoms. The structures of R, Q and Z may be different from each other.

In the general formulas (4-1) to (4-10), R is not particularly limited, but is alkyl having 1 to 40 carbon atoms, cycloalkyl having 4 to 10 carbon atoms, and any hydrogen is halogen or 1 to 1 carbon atoms. Aryl which may be replaced by an alkyl of 20 or an arylalkyl composed of an aryl in which any hydrogen may be replaced by a halogen or an alkyl having 1 to 20 carbon atoms and an alkylene having 1 to 8 carbon atoms. The group selected by Any hydrogen atom may be replaced by a fluorine atom, and any −CH ₂ − may be replaced by −O −, −CH ₂ = CH ₂ − or −CH ₃ ≡ _{CH 3 −.} More specifically, a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a trifluoromethyl group, a hexafluoroisopropyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a vinyl group and an allyl group. , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

In the general formulas (4-1) to (4-10), Q is not particularly limited, but is an alkyl having 1 to 40 carbon atoms, a cycloalkyl having 4 to 10 carbon atoms, and any hydrogen is halogen or 1 to 1 carbon atoms. Independent of aryls that may be replaced by an alkyl of 20 and arylalkyls composed of aryls in which any hydrogen may be replaced by halogens or alkyls having 1 to 20 carbons and alkylenes having 1 to 8 carbons. Is the group that is selected. Any hydrogen atom may be replaced by a fluorine atom, and any −CH ₂ − may be replaced by −O −, −CH ₂ = CH ₂ − or −CH ₃ ≡ _{CH 3 −.} More specifically, a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a trifluoromethyl group, a hexafluoroisopropyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a vinyl group and an allyl group. , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

In the general formulas (4-1) to (4-10), Z specifically includes, but is not limited to, a structure represented by the following structural formula.

The silsesquioxane structure-containing multivalent amine is preferably an amine having a structure represented by the general formulas (4-1) to (4-5) from the viewpoint of easiness of polymerization. The resin (A) preferably contains a cage-type silsesquioxane structure from the viewpoint of compatibility, flattening property, and pattern dimensional stability. That is, it is more preferable to use amines having structures represented by the general formulas (4-1) and (4-2) as raw materials. Further, it is preferable to have a cage-type silsesquioxane structure in the main chain of the resin (A). That is, it is more preferable to use an amine having a structure represented by the general formula (4-1) as a raw material.

<Weakly acidic group having an acid dissociation constant of 13.0 or more and 23.0 or less in dimethyl sulfoxide>
The resin (A) has a weakly acidic group (hereinafter, also referred to as a weakly acidic group) having a pKa in DMSO of 13.0 or more and 23.0 or less at the main chain and / or the terminal of the resin (A). .. By having a weakly acidic group, the photosensitive resin composition can have both flatness and dimensional stability of the pattern at a high level. It is considered that this is because the resin (A) has a weakly acidic group, so that the curing rate by curing can be appropriately adjusted and the reflow of the resin (A) can be controlled.

Examples of the weakly acidic group include an acidic group having a lower acidity as a Bronsted acid than a carboxy group. The acidity of the Bronsted acid corresponds to the carboxy group, and the compound having a carboxy group and the pKa of the compound in DMSO include, for example, acetic acid (pKa = 12.3) or Benzoic acid (pKa = 11.1) can be mentioned.

Examples of the weakly acidic group include a phenolic hydroxyl group, a hexafluoroisopropyl alcohol group, a hydroxyimide group, a hydroxyamide group, a thiol group, and a methylene group in which two or more carbonyl groups or ester groups are bonded. From the viewpoint of dimensional stability of the pattern, the weakly acidic group is preferably at least one selected from the group consisting of a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group and a hexafluoroisopropyl alcohol group, and the phenolic hydroxyl group is more preferable. preferable.

As an index of weak acidity, a compound having an acidic group showing weak acidity, and pKa of the compound in DMSO include, for example, phenol (pKa = 18.0) and hexafluoroisopropyl alcohol (pKa = 17.9). ) Benzohydroxamic acid (pKa = 13.7), n-butanthiol (pKa = 17.0), acetylacetone (pKa = 13.3), ethyl acetoacetate (pKa = 14.2) or diethyl malonate (pKa =) 15.7) can be mentioned.

The content of the weakly acidic group in the resin (A) is 100 mol% of the structural unit represented by the general formula (1-3) in the resin (A) from the viewpoint of flattening property and dimensional stability of the pattern. On the other hand, it is preferably 10 mol% or more and 500 mol% or less.
The content of the weakly acidic group is preferably 500 mol% or less, preferably 300 mol%, based on 100 mol% of the structural unit represented by the general formula (1-3) in the resin (A) from the viewpoint of flattening property. % Or less is more preferable, and 100 mol% or less is further preferable. From the viewpoint of pattern dimensional stability, 10 mol% or more is preferable, 20 mol% or more is more preferable, and 50 mol% or more is further preferable.

In order to obtain the resin (A) having a weakly acidic group at the main chain or the terminal, for example, a weakly acidic group-containing diamine, a weakly acidic group-containing acid dianhydride, a dicarboxylic acid chloride, a dicarboxylic acid active ester, and a weakly acidic group are contained. A residue of at least one diamine, acid dianhydride, monoamine, or acid anhydride selected from the group consisting of monoamine and weakly acidic group-containing acid anhydride may be introduced. Above all, from the viewpoint of easy availability of the monomer, it is preferable to contain a residue of a weakly acidic group-containing diamine and / or a weakly acidic group-containing monoamine. In particular, from the viewpoint of pattern dimensional stability, it is preferable to contain at least a weakly acidic group-containing diamine residue.

The resin (A) preferably has a residue derived from the diamine represented by the general formula (2).

In the general formula (2), X ¹ represents a single bond, an ether bond, a sulfide bond, a disulfide bond, a sulfonyl group, or a divalent organic group having 1 to 200 carbon atoms. X ² and X ³ each independently represent a single bond or a divalent organic group having 1 to 200 carbon atoms. R ² and R ³ each independently represent a monovalent organic group having 1 or more carbon atoms and 200 or less carbon atoms. A ¹ and A ² each independently represent a weakly acidic group having an acid dissociation constant of 13.0 or more and 23.0 or less in dimethyl sulfoxide. a and b are independently integers of 0 or more and 4 or less, and c and d are independently integers of 0 or more and 4 or less, a + b ≧ 1, and 1 ≦ a + b + c + d ≦ 8. X ¹ , X ² , X ³ , R ² , R ³ , A ¹ , and A ² may be different in each of the plurality of repeating units contained in the resin (A).

The resin (A) contains residues derived from at least one type selected from the group consisting of diamines represented by the structural formulas (2A) to (2J) from the viewpoint of flattening property and pattern dimensional stability. It is preferable to have. Among them, one or more selected from the group consisting of diamines represented by the structural formulas (2B), (2C), (2G) and (2H) is more preferable.

Examples of the weakly acidic group-containing monoamine include, but are not limited to, monoamines having a structure represented by the general formula (5).

In the general formula (5), ^{A 3} represents a weakly acidic group. e is an integer of 1 or more and 5 or less. R ⁴ represents a sulfonic acid group or a saturated hydrocarbon group having 1 to 6 carbon atoms, f is 0 or 1. 1 ≦ e + f ≦ 5.

Specifically, as an example of the monoamine represented by the general formula (5), 2-aminophenol, 3-aminophenol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o- Cresol, 4-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 4-amino-2,3-xylenol, 4-amino-3, 5-Xylenol, 6-amino-2,4-xylenol, 2-amino-4-ethylphenol, 3-amino-4-ethylphenol, 2-amino-4-tert-butylphenol, 2-amino-4-phenylphenol , 4-Amino-2,6-diphenylphenol, and compounds having a structure represented by the following structural formula, but are not limited thereto. Of these, 2-aminophenol, 3-aminophenol, and 4-aminophenol are preferable from the viewpoint of pattern dimensional stability.

Examples of the weakly acidic group-containing acid dianhydride include, but are not limited to, acid dianhydride having a structure represented by the following structural formula.

Examples of weakly acidic group-containing acid anhydrides include, but are not limited to, 5-hydroxyisobenzofuran-1,3-dione and 4-hydroxyisobenzofuran-1,3-dione.

Further, the resin (A) may contain a structure derived from another acid dianhydride as long as the above-mentioned properties are not deteriorated. Specific examples of other acid dianhydrides include pyromellitic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, and 9,9-bis (3,4-dicarboxyphenyl). Fluoleic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} Fluoleic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride , Butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2-ethylenebis (anhydrotrimeritate), 1,10-decamethylenebis (anhydride) Known examples such as (hydrotrimeritate) are included, but the present invention is not limited to this. These two or more kinds of acid dianhydride components may be used in combination.

Further, the resin (A) of the present invention may contain a structure derived from another diamine as long as the above-mentioned characteristics are not deteriorated.

Still other diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy). ) Benzene, benzidine, p-phenylenediamine, bis {4- (4-aminophenoxy) phenyl} ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) Aromatic diamines such as -4,4'-diaminobiphenyl, and cyclohexyl, a compound in which some of the hydrogen atoms of these aromatic rings are replaced with alkyl groups, fluoroalkyl groups, halogen atoms, etc. having 1 to 10 carbon atoms. Diamines, alicyclic diamines such as methylenebiscyclohexylamine, "Jeffamine" (registered trademark) ED-600, "Jeffamine" ED-900, "Jeffamine" ED-2003, Polyoxypropylene diamine D-200, Known examples such as aliphatic diamines containing a polyethylene oxide group such as D-400, D-2000, and D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.) can be mentioned, but the present invention is not limited thereto.

These diamines can be used as is or as the corresponding diisocyanate compound, trimethylsilylated diamine. Further, these two or more kinds of diamine components may be used in combination.

An organic group derived from a monoamine or an acid anhydride may be provided at the end of the polymer molecular chain in the resin (A) as an end-capping agent. As the terminal encapsulant, known monoamines and acid anhydrides can be used.

The weight average molecular weight of the resin (A) is preferably 3,000 to 80,000, more preferably 8,000 to 50,000 in terms of polystyrene by gel permeation chromatography.

The resin (A) can be produced according to a known method for producing a polyimide precursor or a polybenzoxazole precursor.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention contains the above-mentioned resin (A), photosensitive compound (B) and solvent (C).

<Photosensitive compound (B)>
Examples of the photosensitive compound (B) include a photoacid generator (b1) and a photopolymerization initiator (b2). The photoacid generator (b1) is a compound that generates acid when irradiated with light and has the property of increasing the solubility of the light-irradiated portion in an alkaline aqueous solution. The photopolymerization initiator (b2) is an exposure. A compound that undergoes bond cleavage and / or reaction to generate radicals.

When the photosensitive compound (B) contains the photoacid generator (b1), acid is generated in the light-irradiated part, the solubility of the light-irradiated part in the alkaline aqueous solution is increased, and the light-irradiated part is dissolved. Relief pattern can be obtained. Further, by containing the photoacid generator (b1) and the epoxy compound or the heat-crosslinking agent described later, the acid generated in the light-irradiated part promotes the cross-linking reaction of the epoxy compound and the heat-crosslinking agent, and the light-irradiated part is insolubilized. It is possible to obtain a negative type relief pattern. Further, when the photosensitive compound (B) contains a photopolymerization initiator (b2) and the photosensitive resin composition further contains a radical polymerizable compound (D) described later, radical polymerization proceeds and the photosensitive resin composition is photosensitive. A negative pattern can be formed by insolubilizing the exposed portion of the film of the resin composition with the alkaline developer.

Examples of the photoacid generator (b1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.

The quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and / or sulfone. Examples thereof include amide-bonded compounds. It is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. Further, it is preferable to contain two or more kinds of photoacid generators (b1), and a highly sensitive photosensitive resin composition can be obtained.

As the photoacid generator, as the quinone diazide, any of a 5-naphthoquinone diazidosulfonyl group and a 4-naphthoquinone diazidosulfonyl group can be preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution and sensitivity are further improved.

Of the photoacid generators (b1), sulfonium salts, phosphonium salts, and diazonium salts are preferable because they appropriately stabilize the acid component generated by exposure. Of these, the sulfonium salt is preferable. Further, a sensitizer or the like can be contained as needed.

In the photosensitive resin composition, the content of the photoacid generator (b1) is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the resin from the viewpoint of increasing sensitivity. Of these, the quinone diazide compound is preferably 3 to 40 parts by mass. The total amount of the sulfonium salt, the phosphonium salt and the diazonium salt is preferably 0.5 to 20 parts by mass.

Examples of the photopolymerization initiator (b2) include a benzyl ketal-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester. Initiators of photopolymerization, aclysin-based photopolymerization, titanosen-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, or benzoic acid ester-based photopolymerization initiators. Agents are preferred, and from the viewpoint of improving sensitivity during exposure, α-hydroxyketone-based photopolymerization initiators, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and acrydin A photopolymerization initiator or a benzophenone-based photopolymerization initiator is more preferable, and an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator are further preferable.

Examples of the α-aminoketone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4). -Morpholinenophenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butane-1-one or 3,6-bis (2-methyl-) Known examples include 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 or bis (2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl) Phosphine oxide and the like are known.

Examples of the oxime ester-based photopolymerization initiator include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime and 1-phenylbutane-1,2-dione-2- (O-methoxy). Oxime of carbonyl, 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-yl] etanone-1- (O-acetyl) oxime, 1- [9-ethyl-6- [2-methyl-4- [1- (2,2-dimethyl-) 1,3-Dioxolan-4-yl) methyloxy] benzoyl] -9H-carbazole-3-yl] etanone-1- (O-acetyl) oxime or 1- (9-ethyl-6-nitro-9H-carbazole- Known examples include 3-yl) -1- [2-methyl-4- (1-methoxypropan-2-yloxy) phenyl] methanone-1- (O-acetyl) oxime.

Also for benzyl ketal photopolymerization initiators, α-hydroxyketone photopolymerization initiators, aclysin photopolymerization initiators, titanosen photopolymerization initiators, acetophenone photopolymerization initiators, and benzoic acid ester photopolymerization initiators. Known initiators can be used.

In the photosensitive resin composition, the content of the photopolymerization initiator (b2) is 0.1 part by mass or more when the total of the resin (A) and the radically polymerizable compound (D) described later is 100 parts by mass. Is preferable, 0.5 parts by mass or more is more preferable, 0.7 parts by mass or more is further preferable, and 1 part by mass or more is particularly preferable. When the content is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is within the above range, the resolution after development can be improved and a pattern shape having a low taper can be obtained.

<Solvent (C)>
The photosensitive resin composition contains the solvent (C).
Examples of the solvent (C) include ethers such as ethylene glycol monomethyl ether propylene glycol monomethyl ether, esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate, ethanol, and the like. Alcohols such as isopropanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, diacetone alcohol, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylisobutylamide, 3-methoxy Known examples include polar aproton solvents such as −N, N-dimethylpropionamide, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. The content of the solvent (C) is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1500 parts by mass with respect to 100 parts by mass of the resin (A). It is less than a part by mass.

<Radical polymerizable compound (D)>
When the photosensitive compound (B) contains a photopolymerization initiator (b2), the photosensitive resin composition preferably further contains a radically polymerizable compound (D).

The radically polymerizable compound (D) refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule. At the time of exposure, radical polymerization of the radically polymerizable compound (D) proceeds by the radicals generated from the above-mentioned photopolymerization initiator (b2), and the exposed portion of the film of the photosensitive resin composition becomes insoluble in the alkaline developing solution. By doing so, a negative pattern can be formed.

By containing the radically polymerizable compound (D), UV curing at the time of exposure is promoted, and the sensitivity at the time of exposure can be improved. In addition, the crosslink density after thermosetting is improved, and the hardness of the cured product can be improved.

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

Examples of the radically polymerizable compound (D) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and trimethyl propantri (d). Meta) 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, 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 1,3,5-tris ((meth) acryloxyethyl) isocyanuric acid, 1 , 3-Bis ((meth) acryloxyethyl) isocyanuric acid, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis [4- (3- (meth) acryloxyethoxy) phenyl] ) Acryloxypropoxy) phenyl] fluorene or 9,9-bis (4- (meth) acryloxiphenyl) fluorene or an acid-modified product thereof, an ethylene oxide-modified product, a propylene oxide-modified product, or the like.

From the viewpoint of improving the resolution after development, those acid-modified products or ethylene oxide-modified products are preferable. Further, from the viewpoint of improving the resolution after development, a compound obtained by ring-opening addition reaction of a compound having two or more glycidoxy groups in the molecule and an unsaturated carboxylic acid having an ethylenically unsaturated double bond group. A compound obtained by reacting a polybasic carboxylic acid or a polybasic carboxylic acid anhydride is also preferable.

In the photosensitive resin composition, the content of the radically polymerizable compound (D) is preferably 15 parts by mass or more, preferably 20 parts by mass or more, when the total of the resin (A) and the radically polymerizable compound (D) is 100 parts by mass. It is more preferably parts by mass or more, more preferably 25 parts by mass or more, and particularly preferably 30 parts by mass or more. When the content is within the above range, the sensitivity at the time of exposure can be improved and a pattern shape having a low taper can be obtained. On the other hand, the content is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, further preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content is within the above range, the heat resistance of the cured product can be improved and a pattern shape having a low taper can be obtained. By making the pattern shape low taper, it is possible to improve the drive stability of the completed organic EL panel.

<Thermal cross-linking agent (E)>
The photosensitive resin composition can further contain the thermal cross-linking agent (E).
The thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group. The thermosetting agent can crosslink the resin (A) or other additive components to increase the heat resistance, chemical resistance and hardness of the film after thermosetting.

Preferred examples of the compound having at least two alkoxymethyl groups or trimethylol groups include, for example, DMOM-PC, TriML-P, TMOM-BP, HML-TPPHBA, HMOM-TPPHBA, (hereinafter, trade name, Honshu Chemical Industry Co., Ltd.). (Manufactured by Sanwa Chemical Co., Ltd.), NIKARAC MX-270, (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like.

Examples of the compound having an epoxy group or an oxetanyl group include "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), VG3101L (trade name, Co., Ltd.). ) Printec), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (trade name, manufactured by Nissan Chemical Industry Co., Ltd.), OXT-121, OXT-221, OX-SQ- Known examples include H, OXT-191, PNOX-1009, RSOX (trade name, manufactured by Toagosei Co., Ltd.) and the like.

When the content of the thermal cross-linking agent (E) is 5 parts by mass or more with respect to 100 parts by mass of the resin (A), the cross-linking density becomes high and the chemical resistance is improved, which is preferable. Further, when it is 10 parts by mass or more, higher mechanical properties can be obtained. On the other hand, from the viewpoint of storage stability and mechanical strength of the composition, 50 parts by mass or less is preferable, 40 parts by mass or less is more preferable, and 30 parts by mass or less is further preferable.

<Colorant>
The photosensitive resin composition may further contain a colorant.

The colorant is a compound that absorbs light having a specific wavelength, and particularly refers to a compound that colors by absorbing light having a wavelength of visible light (380 to 780 nm).

By containing a colorant, the film obtained from the photosensitive resin composition can be colored, and the light transmitted through the film of the photosensitive resin composition or the light reflected from the film of the photosensitive resin composition can be emitted. , It is possible to impart colorability to color a desired color. Further, it is possible to impart a light-shielding property that blocks light having a wavelength absorbed by the colorant from the light transmitted through the film of the photosensitive resin composition or the light reflected from the film of the photosensitive resin composition.

Examples of the colorant include compounds that absorb light having a wavelength of visible light and color white, red, orange, yellow, green, blue, purple, and black. By combining two or more colors, the light transmitted through the film of the desired photosensitive resin composition of the photosensitive resin composition or the light reflected from the film of the photosensitive resin composition is toned to the desired color coordinates. It is possible to improve the toning property.

The colorant is preferably a pigment and / or dye described below.
Further, the colorant is preferably a black colorant.
When a colorant is contained, a known dispersant may also be contained.

<Compound with phenolic hydroxyl group>
The photosensitive resin composition may contain a compound having a phenolic hydroxyl group for the purpose of supplementing the alkali developability of the photosensitive resin composition, if necessary. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, TekP-4HBPA (Tetrakiss P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, (hereinafter, trade name, Honshu Chemical Industry Co., Ltd.). (Available from Asahi Organic Materials Co., Ltd.), BIR-OC, BIP-PCBIR-PC, (above, trade name, available from Asahi Organic Material Industry Co., Ltd.) and the like.

<Resin other than resin (A)>
The photosensitive resin composition may contain a resin other than the resin (A). Specifically, polyamide, an acrylic polymer copolymerized with acrylic acid, a novolak resin, a resole resin, a siloxane resin, a polyhydroxystyrene resin, and a resin in which a cross-linking group such as a methylol group, an alkoxymethyl group or an epoxy group is introduced. , Their copolymerized polymers and the like. When the resin (A) is used in combination with another resin, the amount of the resin (A) is preferably 30% by mass or more with respect to 100% by mass of the total resin contained in the photosensitive resin composition.

The photosensitive resin composition may further appropriately contain known sensitizers, chain transfer agents, polymerization inhibitors, adhesion improvers, surfactants, thermoacid generators, thermobase generators, inorganic particles and the like. ..

<Manufacturing method of photosensitive resin composition>
Next, a method for producing the photosensitive resin composition will be described. For example, the resin (A), the photosensitive compound (B), and the solvent (C) component of the present invention, and if necessary, a thermal cross-linking agent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, and inorganic particles. , A photosensitive resin composition can be obtained by dissolving a thermal acid generator or the like. Examples of the melting method include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C. Further, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.

The obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dust and particles. The filter pore diameter is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, and the like, but is not limited thereto. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTEE) and the like, but polyethylene and nylon are preferable.

<Cured product>
The cured product of the present invention is a cured product of the photosensitive resin composition.
In order to cure the photosensitive resin composition, the photosensitive resin composition may be heat-cured. Since components having low heat resistance can be removed by heat curing, the heat resistance and chemical resistance of the cured product can be improved. In particular, when the resin (A) contained in the photosensitive resin composition contains a structural unit of a polyimide precursor or a polybenzoxazole precursor, an imide ring and an oxazole ring can be formed by heat curing, so that heat resistance and resistance are obtained. The chemical properties can be improved, and when a compound having at least two or more alkoxymethyl groups, polyimide groups, epoxy groups, or octanyl groups is contained, the thermal cross-linking reaction can be promoted by heat curing, and heat resistance can be improved. The property and chemical resistance can be improved.

This heat curing is carried out for 5 minutes to 5 hours while selecting a certain temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 150 ° C. and 250 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 300 ° C. over 2 hours can be mentioned. As the heat curing conditions, 300 ° C. or higher is preferable, and 350 ° C. or higher is more preferable, in terms of reducing the amount of outgas generated from the cured product. Further, 500 ° C. or lower is preferable, and 450 ° C. or lower is more preferable, from the viewpoint of giving sufficient film toughness to the cured product.

<Manufacturing method of cured product>
A method for producing a cured product using the photosensitive resin composition of the present invention will be described in detail.
The obtained cured product can be suitably used as a gate insulating layer or an interlayer insulating layer of a thin film transistor.

The method for producing a cured product using the photosensitive resin composition includes a step of applying the photosensitive resin composition on a substrate to form a photosensitive resin film, a step of drying the photosensitive resin film, and a dried photosensitive resin film. It includes a step of exposing the resin film, a step of developing the exposed photosensitive resin film, and a step of heat-treating the developed photosensitive resin film to obtain a cured product.

Details of each process will be described below.
The process of applying the photosensitive resin composition on the substrate to form the photosensitive resin film will be described. The photosensitive resin composition is applied onto a substrate by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like to obtain a coating film of the photosensitive resin composition. Of these, the slit coat method is preferably used. The film thickness of the coating film varies depending on the solid content concentration, viscosity, etc. of the photosensitive resin composition, but is usually applied so that the film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm. NS.

Prior to coating, the substrate to which the photosensitive resin composition is applied may be pretreated with the above-mentioned adhesion improving agent in advance. For example, a solution in which the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass is used. Then, a method of treating the surface of the base material can be mentioned. Examples of the method for treating the surface of the base material include methods such as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

Next, the step of drying the photosensitive resin film will be described.
After coating, if necessary, perform vacuum drying treatment. For example, a substrate on which a coating film is formed is placed on a proxy pin arranged in a vacuum chamber, and the inside of the vacuum chamber is depressurized to dry under reduced pressure. The vacuum drying rate depends on the volume of the vacuum chamber, the capacity of the vacuum pump, the diameter of the pipe between the chamber and the pump, etc. Set and used. The general vacuum drying time is often about 30 seconds to 100 seconds, and the pressure reached in the vacuum chamber at the end of vacuum drying is usually 100 Pa or less with the coated substrate. After coating or drying under reduced pressure, the coating film is generally heat-dried. This process is also called prebaking. Use a hot plate, oven, infrared rays, etc. for drying. When a hot plate is used, the coating film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. The heating temperature varies depending on the type and purpose of the coating film, and is preferably carried out in the range of 50 ° C. to 180 ° C. for 1 minute to several hours.

Next, a step of exposing the dried photosensitive resin film will be described.
The photosensitive resin film is exposed to chemical rays by irradiating it with a chemical line through a mask having a desired pattern. Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. .. When it has positive photosensitivity, the exposed part dissolves in the developer. When it has a negative photosensitive property, the exposed portion is cured and insolubilized in a developing solution.

Next, a step of developing the exposed photosensitive resin film will be described.
After the exposure, a desired pattern is formed by removing the exposed portion in the case of the positive type and the non-exposed portion in the case of the negative type using a developing solution. As the developer, an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, or potassium hydroxide is preferable in both positive and negative types. In some cases, these alkaline aqueous solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone and dimethylacrylamide, alcohols such as methanol, ethanol and isopropanol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate. , Cyclopentanone, Cyclohexanone, Isobutyl Ketone, Methyl Isobutyl Ketone and other ketones may be added alone or in combination of several types. As the developing method, a spray, paddle, immersion, ultrasonic wave or the like can be used.

Next, it is preferable to rinse the pattern formed by development with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.

Next, a step of heat-treating the developed photosensitive resin film to obtain a cured product will be described.
Since components having low heat resistance can be removed by heat curing, the heat resistance and chemical resistance of the cured product can be improved. In particular, when the resin (A) contained in the photosensitive resin composition contains a structural unit of a polyimide precursor or a polybenzoxazole precursor, an imide ring and an oxazole ring can be formed by heat curing, so that heat resistance and resistance are obtained. The chemical properties can be improved, and when a compound having at least two or more alkoxymethyl groups, polyimide groups, epoxy groups, or octanyl groups is contained, the thermal cross-linking reaction can be promoted by heat curing, and heat resistance can be improved. The property and chemical resistance can be improved. This heat curing is carried out for 5 minutes to 5 hours while selecting a certain temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 150 ° C. and 250 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 300 ° C. over 2 hours can be mentioned. As the heat curing conditions, 300 ° C. or higher is preferable, and 350 ° C. or higher is more preferable, in terms of reducing the amount of outgas generated from the cured product. Further, 500 ° C. or lower is preferable, and 450 ° C. or lower is more preferable, from the viewpoint of giving sufficient film toughness to the cured product.

A cured product obtained by curing a photosensitive resin composition using the resin (A) of the present invention can be used for an organic EL display device, a semiconductor device, a multilayer wiring board, or the like. Specifically, the insulating layer of the organic EL display device, the flattening layer of the substrate with the drive circuit of the organic EL display device, the interlayer insulating film between the rewiring of the semiconductor device, the passive film of the semiconductor, the protective film of the semiconductor device, and the height. It is suitably used for applications such as an interlayer insulating film for multi-layer wiring for density mounting, a wiring protective insulating layer for a circuit board, an on-chip microlens for a solid-state imaging device, and a flattening layer for various displays and solid-state imaging devices. Hereinafter, an organic EL display device will be described as an example.

<Organic EL display device>
The organic EL display device of the present invention comprises the cured product.
Specifically, the substrate has a flattening layer, a first electrode, a pixel dividing layer, an organic EL layer, and a second electrode, and the flattening layer and / or the pixel dividing layer contains the cured product of the present invention. It is an organic EL display device. Taking an active matrix type display device as an example, a TFT (thin film transistor) is provided on a substrate such as glass or a resin film, and wiring located on the side of the TFT and connected to the TFT is provided on the TFT (thin film transistor). A flattening layer is provided so as to cover the unevenness, and a display element is further provided on the flattening layer. The display element and the wiring are connected via a contact hole formed in the flattening layer. A cured product obtained by curing the photosensitive resin composition of the present invention is preferably used as a flattening layer because it has excellent flatness and pattern dimensional stability. In particular, in recent years, flexible organic EL display devices have become mainstream, and the substrate having the above-mentioned drive circuit may be an organic EL display device made of a resin film.

<Semiconductor device>
The semiconductor device of the present invention comprises the above-mentioned cured product.

Specifically, it is a semiconductor device in which the cured product of the present invention is contained in an insulating film and / or a protective film in the structure of a known semiconductor device. The cured product obtained by curing the photosensitive resin composition of the present invention is excellent in flattening property and pattern dimensional stability, and is therefore preferably used for the above-mentioned insulating film and / or protective film.

Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. The photosensitive resin composition in the examples was evaluated by the following method.

<Measurement method of film thickness>
Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness after prebaking, developing, and curing was measured with a refractive index of 1.629 for polyimide.

(1-1) Flatness Evaluation of Positive Photosensitive Resin Composition FIG. 1 shows a cross-sectional view of a flatness evaluation sample. The photosensitive resin compositions (varnishes) prepared in Examples 1 to 27 and Comparative Examples 1 to 4 are spun on a stepped substrate 1 in which five line patterns having a thickness of 1 μm and a width of 5 μm are patterned in parallel at intervals of 5 μm. Rotate coating with a coater (Opticoat MS-B150; manufactured by Mikasa Co., Ltd.), then bake on a hot plate (DIGITAL HOT PLLET HP-18A; manufactured by AS ONE Co., Ltd.) at 120 ° C. for 2 minutes to a thickness of 2.5 μm. A pre-baked film was prepared. This prebaked film is heated to 250 ° C. at 5 ° C./min at an oxygen concentration of 20 ppm or less using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.) and heat-treated at 250 ° C. for 1 hour. A cured product 2 of the varnish was prepared by performing a heat curing step. The surface steps h1 to h3 of the obtained cured product 2 were measured with a surface profiler (P.15; KLA Tencor Co., Ltd.), and the average value of h1 to h3 was taken as the surface step h. The surface step h after the heat curing step is A + if it is less than 0.03 μm, A if it is 0.03 μm or more and less than 0.10 μm, B + if it is 0.10 μm or more and less than 0.15 μm, and 0.15 μm or more 0. .20 μm or less was judged as B, 0.20 μm or more and less than 0.25 μm was judged as C +, 0.25 μm or more and less than 0.30 μm was judged as C, and 0.3 μm or more was judged as D.

(1-2) Evaluation of Flatness of Negative Photosensitive Resin Composition Using the photosensitive resin compositions (varnish) prepared in Examples 28 to 29 and Comparative Examples 5 to 6, the temperature of the hot plate was changed to 100 ° C. The evaluation was carried out in the same manner as in (1-1) above, except that

(2-1) Evaluation of Dimensional Stability of Positive Photosensitive Resin Composition The photosensitive resin composition (varnish) prepared in Examples 1 to 27 and Comparative Examples 1 to 4 was rotationally coated on an 8-inch silicon wafer. Next, it was baked on a hot plate at 120 ° C. (using a coating developer Act-8 manufactured by Tokyo Electron Limited) for 2 minutes to prepare a prebaked film having a thickness of about 2.5 μm. The membrane was exposed at 10 mJ / cm ² steps at an exposure amount ranging 0~1000mJ / cm ² using an i-line stepper (NIKON NSR i9). After exposure, develop with 2.38 mass% tetramethylammonium (TMAH) aqueous solution (ELM-D manufactured by Mitsubishi Gas Chemical Company, Inc.) for 10 to 300 seconds, then rinse with pure water to form a hole with a diameter of about 5 μm. A developing film having a pattern and having a film thickness of about 2 μm was obtained. Subsequently, the developing film is heated to 250 ° C. at 5 ° C./min at an oxygen concentration of 20 ppm or less using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.), and 1 at 250 ° C. A cured product of varnish was prepared by performing a curing step of heat treatment for a time.

Using a digital microscope (VHX-6000; manufactured by KEYENCE CORPORATION), the opening size of a hole pattern having a diameter of 5 μm before and after the curing process was measured, and ΔCD (opening size before curing-opening size after curing) was determined. .. ΔCD of less than 0.10 μm is A, those of 0.10 μm or more and less than 0.15 μm are B +, those of 0.15 μm or more and less than 0.20 μm are B, and those of 0.20 μm or more and less than 0.25 μm are C +. , 0.25 μm or more and less than 0.30 μm was judged as C, and 0.3 μm or more was judged as D.

(2-2) Evaluation of Dimensional Stability of Negative Photosensitive Resin Composition The photosensitive resin composition (varnish) prepared in Examples 28 to 29 and Comparative Examples 5 to 6 was rotationally coated on an 8-inch silicon wafer. Next, it was baked on a hot plate at 100 ° C. (using a coating developer Act-8 manufactured by Tokyo Electron Limited) for 2 minutes to prepare a prebaked film having a thickness of about 2.0 μm. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~1000mJ / cm ² using an i-line stepper (NIKON NSR i9). After exposure, develop with 2.38 mass% tetramethylammonium (TMAH) aqueous solution (ELM-D manufactured by Mitsubishi Gas Chemical Company, Inc.) for 10 to 300 seconds, then rinse with pure water to form a hole with a diameter of about 5 μm. A developing film having a pattern and having a film thickness of about 2 μm was obtained. Subsequently, the developing film is heated to 250 ° C. at 5 ° C./min at an oxygen concentration of 20 ppm or less using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.), and 1 at 250 ° C. A cured product of varnish was prepared by performing a curing step of heat treatment for a time.

Using a digital microscope (VHX-6000; manufactured by KEYENCE CORPORATION), the opening size of a hole pattern having a diameter of 5 μm before and after the curing process was measured, and ΔCD (opening size before curing-opening size after curing) was determined. .. ΔCD of less than 0.10 μm is A, those of 0.10 μm or more and less than 0.15 μm are B +, those of 0.15 μm or more and less than 0.20 μm are B, and those of 0.20 μm or more and less than 0.25 μm are C +. , 0.25 μm or more and less than 0.30 μm was judged as C, and 0.3 μm or more was judged as D.

Those whose flatness evaluation results are A + to C and whose dimensional stability evaluation results are A to C are accepted, and those whose flatness evaluation result or at least one of the dimensional stability evaluation results is D are accepted. It was judged as a failure.

The names of abbreviations for acid dianhydrides, diamines, and other reagents shown in the following examples and comparative examples are as follows.
APDMMS: 3-aminopropyldimethylmethoxysilane BAHF: 2,2-bis (3-amino-4-hydroxyphenyl) Hexafluoropropane Bis-AT-AF: 2,2-bis (3-amino-4-methylphenyl) Hexafluoropropane BPDC: 4,4'-biphenyldicarbonyl chloride DFA: N, N-dimethylformamide dimethylacetal DPHA: "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd .; dipentaerythritol hexaacrylate)
HFA-MDA: 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -methylenedianiline MAP: 3-aminophenol; metaaminophenol MBA: 3-methoxy -N-Butylacetate NCI-831: "Adecaarclus" (registered trademark) NCI-831 (manufactured by ADEKA Co., Ltd .; 1- (9-ethyl-6-nitro-9H-carbazole-3-yl) -1- (9-ethyl-6-nitro-9H-carbazole-3-yl) -1- [2-Methyl-4- (1-methoxypropan-2-yloxy) phenyl] Metanon-1- (O-acetyl) oxime)
NMP: N-methyl-2-pyrrolidone ODPA: 4,4'-oxydiphthalic acid dianhydride PTMS: Phenyltrimethoxysilane TAC: Trimellitic anhydride chloride Chloride MX-270 (E-) used in each Example and Comparative Example 1) is shown below.

<Synthesis Example 1 Synthesis of Hydroxy Group-Containing Diamine Compound (HA)>
18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide and cooled to −15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropping, the reaction was carried out at −15 ° C. for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

30 g of the obtained white solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced into this with a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HA) represented by the following formula. The obtained solid was used as it was in the reaction.

<Synthesis Example 2 Synthesis of quinonediazide compound (QD-1)>
21.23 g (0.05 mol) of TrisP-PA in a three-necked flask under a dry nitrogen stream.
), 5-Naftquinonediazide sulfonic acid chloride was weighed in 37.62 g (0.14 mol) and dissolved in 450 g of 1,4-dioxane to bring it to room temperature. Here, a mixed solution of 50 g of 1,4-dioxane and 15.58 g (0.154 mol) of triethylamine was added to 3 in the system.
The mixture was added dropwise with stirring so as not to exceed 5 ° C. After completion of the dropping, the mixed solution was stirred at 30 ° C. for 2 hours. After stirring, the precipitated triethylamine salt was removed by filtration, and then the filtrate was added to water for stirring, and the precipitated solid precipitate was obtained by filtration. The obtained solid was dried under reduced pressure to obtain a compound (QD-1) having a naphthoquinone diazide structure having the following structure.

<Synthesis Example 3> Synthesis of Silsesquioxane-Containing Monomer (S-1)>
The silsesquioxane-containing monomer (S-1) was synthesized by the method described in JP-A-2007-302635.

<Synthesis Example 4> Synthesis of Silsesquioxane-Containing Monomer (S-2)>
The silsesquioxane-containing monomer (S-2) was synthesized by the method described in JP-A-2004-331647.

<Synthesis Example 5> Synthesis of Silsesquioxane-Containing Monomer (S-3)>
The silsesquioxane-containing monomer (S-3) was synthesized by using SO1450-TriSilanolisobutylPOSS (manufactured by Hybrid Plastic Co., Ltd.) as a raw material and referring to the method described in JP-A-2005-232024.

<Synthesis Example 6> Synthesis of Silsesquioxane-Containing Monomer (S-4)>
Under a dry nitrogen stream, 500 g of toluene was added to 52.1 g (0.040 mol) of the compound (S-4-1) synthesized by the method described in JP-A-2017-078103, and a Karstedt's catalyst (2 wt% toluene) was added. After adding 25 μL of the solution), the temperature of the reaction solution was raised to 80 ° C. To this, 30.1 g (0.17 mol) of allyl-p-nitrophenyl ether synthesized by the method described in JP-A-2004-331647 was added dropwise, and the mixture was stirred at 80 ° C. for 24 hours. After allowing to cool, 100 g of toluene and 300 g of water were added for extraction. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluting solvent: toluene). Toluene was distilled off under reduced pressure and then recrystallized from ethanol / ethyl acetate to obtain compound (S-4-2).

Under a hydrogen atmosphere, a mixture of 14.1 g (0.007 mol) of compound (S-4-2), Pd / C (2 g) and 100 g of THF synthesized as described above was stirred at 30 ° C. for 200 hours. After filtering Pd / C, THF was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluting solvent: ethyl acetate). Ethyl acetate was distilled off under reduced pressure to obtain a silsesquioxane-containing monomer (S-4).

[Example 1]
Under a dry nitrogen stream, 5.49 g (0.015 mol) of BAHF was dissolved in 20 g of NMP. To this, 8.89 g (0.006 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 10 g of NMP, then 2.79 g (0.009 mol) of ODPA was added together with 15 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 3.6 g (0.03 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-1).

10 g of the obtained resin (A-1), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) are added to 50 g of GBL for positive photosensitive. A varnish A1 of a resin composition was obtained. Using the obtained varnish A1, the flatness evaluation and the pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 2]
Under a dry nitrogen stream, 7.70 g (0.021 mol) of BAHF and 3.26 g (0.009 mol) of Bis-AT-AF were dissolved in 20 g of NMP. To this, 13.34 g (0.009 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 15 g of NMP, then 6.52 g (0.021 mol) of ODPA was added together with 15 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 7.2 g (0.06 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-2).

10 g of the obtained resin (A-2), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A2 of a resin composition was obtained. Using the obtained varnish A2, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 3]
Under a dry nitrogen stream, 7.69 g (0.021 mol) of BAHF and 3.26 g (0.009 mol) of Bis-AT-AF were dissolved in 20 g of NMP. To this, 8.89 g (0.006 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 9 g of NMP, then 7.45 g (0.024 mol) of ODPA was added together with 10 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 7.2 g (0.06 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-3).

10 g of the obtained resin (A-3), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A3 of a resin composition was obtained. Using the obtained varnish A3, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 4]
Under a dry nitrogen stream, 7.33 g (0.020 mol) of BAHF was dissolved in 20 g of NMP. To this, 2.96 g (0.002 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 10 g of NMP, then 5.58 g (0.018 mol) of ODPA was added together with 12 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 4.8 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-4).

10 g of the obtained resin (A-4), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A4 of a resin composition was obtained. Using the obtained varnish A4, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 5]
Under a dry nitrogen stream, 7.33 g (0.020 mol) of BAHF was dissolved in 20 g of NMP. To this, 1.19 g (0.0008 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 9 g of NMP, then 5.96 g (0.0192 mol) of ODPA was added together with 10 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 4.8 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-5).

10 g of the obtained resin (A-5), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A5 of a resin composition was obtained. Using the obtained varnish A5, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 6]
Under a dry nitrogen stream, 5.12 g (0.014 mol) of BAHF and 2.18 g (0.006 mol) of Bis-AT-AF were dissolved in 30 g of NMP. To this, 23.92 g (0.016 mol) of the silsesquioxane structure-containing monomer (S-1) was added together with 15 g of NMP, and then 1.24 g (0.004 mol) of ODPA was stirred at 40 ° C. for 8 hours. Then, 4.8 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-6).

10 g of the obtained resin (A-6), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A6 of a resin composition was obtained. Using the obtained varnish A6, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 7]
Under a dry nitrogen stream, 2.56 g (0.007 mol) of BAHF and 2.54 g (0.007 mol) of Bis-AT-AF were dissolved in 30 g of NMP. To this, 20.8 g (0.014 mol) of the silsesquioxane structure-containing monomer (S-1) was added together with 20 g of NMP, and then the mixture was stirred at 40 ° C. for 8 hours. Then, 3.3 g (0.028 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-7).

10 g of the obtained resin (A-7), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A7 of a resin composition was obtained. Using the obtained varnish A7, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 8]
Under a dry nitrogen stream, 1.83 g (0.003 mol) of BAHF and 1.81 g (0.007 mol) of Bis-AT-AF were dissolved in 20 g of NMP. After adding 14.9 g (0.010 mol) of the silsesquioxane structure-containing monomer (S-1) together with 10 g of NMP, the mixture was stirred at 40 ° C. for 8 hours. Then, 2.4 g (0.02 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-8).

10 g of the obtained resin (A-8), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A8 of a resin composition was obtained. Using the obtained varnish A8, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 9]
Under a dry nitrogen stream, 5.81 g (0.004 mol) of silsesquioxane structure-containing monomer (S-2) and 4.40 g (0.012 mol) of BAHF were dissolved in 20 g of NMP. To this, 4.96 g (0.016 mol) of ODPA was added together with 17 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. Then, 3.8 g (0.032 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-9).

10 g of the obtained resin (A-9), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A9 was obtained. Using the obtained varnish A9, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 10]
7.96 g (0.008 mol) of silsesquioxane structure-containing monomer (S-3) and 8.80 g (0.024 mol) of BAHF were dissolved in 30 g of NMP under a dry nitrogen stream. To this, 9.92 g (0.032 mol) of ODPA was added together with 30 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. Then, 7.6 g (0.064 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-10).

10 g of the obtained resin (A-10), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A10 of a resin composition was obtained. Using the obtained varnish A10, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 11]
Under a dry nitrogen stream, 9.17 g (0.005 mol) of silsesquioxane structure-containing monomer (S-4) and 5.49 g (0.015 mol) of BAHF were dissolved in 30 g of NMP. To this, 6.20 g (0.020 mol) of ODPA was added together with 12 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. Then, 4.3 g (0.036 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-11).

10 g of the obtained resin (A-11), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A9 was obtained. Using the obtained varnish A9, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 12]
Under a dry nitrogen stream, 5.50 g (0.010 mol) of HFA-MDA was dissolved in 20 g of NMP. To this, 5.93 g (0.004 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 10 g of NMP, then 1.86 g (0.006 mol) of ODPA was added together with 5 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 2.4 g (0.02 mol) of DEA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-12).

10 g of the obtained resin (A-12), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (d-1) were added to 50 g of GBL for positive photosensitive. A varnish A12 of a resin composition was obtained. Using the obtained varnish A12, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 13]
Under a dry nitrogen stream, 4.57 g (0.0126 mol) of Bis-AT-AF was dissolved in 20 g of NMP. To this, 4.00 g (0.0027 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 10 g of NMP, then 4.75 g (0.0153 mol) of ODPA was added together with 7 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. bottom. Then, 1.18 g (0.108 mol) of MAP was added together with 3 g of NMP, and the mixture was stirred at 40 ° C. for 6 hours. 4.3 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-13).

10 g of the obtained resin (A-13), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A13 of a resin composition was obtained. Using the obtained varnish A13, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 14]
29.74 g (0.15 mol) of phenyltrimethoxysilane and 2.95 g (0.02 mol) of dimethoxy3-aminopropyldimethylmethoxysilane were dissolved in 50 g of NMP under a dry nitrogen stream. 8.46 g (0.47 mol) of distilled water was added thereto, and the mixture was stirred at 60 ° C. for 2 hours. Subsequently, 14.52 g (0.01 mol) of the silsesquioxane structure-containing monomer (S-2) and 10.87 g (0.03 mol) of Bis-AT-AF were added together with 10 g of NMP, and then 15.51 g (0) of ODPA. 0.05 mol) was added with 15 g of NMP and stirred at 40 ° C. for 2 hours. 11.9 g (0.10 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-14).

10 g of the obtained resin (A-14), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A14 was obtained. Using the obtained varnish A14, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 4.

[Example 15]
Under a dry nitrogen stream, 10.71 g (0.0540 mol) of phenyltrimethoxysilane and 3.18 g (0.0216 mol) of 3-aminopropyldimethylmethoxysilane were dissolved in 50 g of NMP. 3.3 g (0.183 mol) of distilled water was added thereto, and the mixture was stirred at 60 ° C. for 2 hours. Subsequently, 7.92 g (0.0216 mol) of BAHF and 7.83 g (0.0216 mol) of Bis-AT-AF were added together with 10 g of NMP, and 16.75 g (0.0540 mol) of ODPA was added together with 20 g of NMP at 40 ° C. The mixture was stirred for 2 hours. 12.9 g (0.11 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-15).

10 g of the obtained resin (A-15), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A15 of the resin composition was obtained. Using the obtained varnish A15, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 16]
Synthesized in the same manner as in Example 15 except that 7.92 g (0.0216 mol) of BAHF was changed to 15.84 g (0.432 mol) and 7.83 g (0.0216 mol) of Bis-AT-AF was not added. Then, a resin (A-16) was obtained.

10 g of the obtained resin (A-16), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A16 of a resin composition was obtained. Using the obtained varnish A16, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 17]
Except for changing BAHF 7.92 g (0.0216 mol) to 1.98 g (0.0056 mol) and Bis-AT-AF 7.83 g (0.0216 mol) to 13.70 g (0.0378 mol). Was synthesized in the same manner as in Example 15 to obtain a resin (A-17).

10 g of the obtained resin (A-17), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A17 of a resin composition was obtained. Using the obtained varnish A17, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 18]
Resin (A-18) was obtained by synthesizing in the same manner as in Example 12 except that 7.92 g (0.0216 mol) of BAHF was changed to 11.89 g (0.0216 mol) of HFA-MDA.

10 g of the obtained resin (A-18), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A18 of the resin composition was obtained. Using the obtained varnish A18, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 19]
Under a dry nitrogen stream, 10.71 g (0.0540 mol) of phenyltrimethoxysilane and 3.18 g (0.0216 mol) of 3-aminopropyldimethylmethoxysilane were dissolved in 50 g of NMP. 3.3 g (0.183 mol) of distilled water was added thereto, and the mixture was stirred at 60 ° C. for 2 hours. Subsequently, 9.78 g (0.0270 mol) of Bis-AT-AF was added together with 10 g of NMP, 16.75 g (0.0540 mol) of ODPA was added together with 20 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. Then, 3.54 g (0.0324 mol) of MAP was added together with 3 g of NMP, and the mixture was stirred at 40 ° C. for 6 hours. 12.9 g (0.11 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-19).

10 g of the obtained resin (A-19), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A19 was obtained. Using the obtained varnish A19, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 20]
29.74 g (0.15 mol) of phenyltrimethoxysilane and 2.95 g (0.02 mol) of dimethoxy3-aminopropyldimethylmethoxysilane were dissolved in 50 g of NMP under a dry nitrogen stream. 8.46 g (0.47 mol) of distilled water was added thereto, and the mixture was stirred at 60 ° C. for 2 hours. Subsequently, 14.49 g (0.04 mol) of Bis-AT-AF was added together with 10 g of NMP, then 15.51 g (0.05 mol) of ODPA was added together with 15 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. 11.9 g (0.10 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-20).

10 g of the obtained resin (A-20), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A20 of a resin composition was obtained. Using the obtained varnish A20, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 21]
Under a dry nitrogen stream, 5.86 g (0.016 mol) of BAHF was dissolved in 20 g of NMP. To this, 5.92 g (0.004 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 10 g of NMP, then 4.96 g (0.016 mol) of ODPA was added together with 7 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. bottom. Then, 0.87 g (0.008 mol) of MAP was added together with 3 g of NMP, and the mixture was stirred at 40 ° C. for 6 hours. 4.8 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-21).

10 g of the obtained resin (A-21), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A21 was obtained. Using the obtained varnish A21, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 22]
Under a dry nitrogen stream, 5.12 g (0.014 mol) of BAHF and 5.40 g (0.006 mol) of "Jeffamine" ED-900 (manufactured by HUNTSMAN Corporation) were dissolved in 30 g of NMP. To this, 8.90 g (0.006 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 15 g of NMP, then 4.34 g (0.014 mol) of ODPA was added together with 4 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 4.8 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-22).

10 g of the obtained resin (A-22), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A22 was obtained. Using the obtained varnish A22, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 23]
Under a dry nitrogen stream, 3.66 g (0.010 mol) of BAHF and 6.04 g (0.010 mol) of the hydroxyl group-containing diamine compound (HA) obtained in Synthesis Example 1 were dissolved in 30 g of NMP. To this, 11.86 g (0.008 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 15 g of NMP, then 3.72 g (0.012 mol) of ODPA was added together with 10 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. bottom. Then, 4.8 g (0.04 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-23).

10 g of the obtained resin (A-23), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A23 was obtained. Using the obtained varnish A23, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 24]
Under a dry nitrogen stream, 7.34 g (0.020 mol) of BAHF was dissolved in 30 g of NMP. To this, 11.86 g (0.008 mol) of silsesquioxane structure-containing monomer (S-1) was added together with 15 g of NMP, then 3.72 g (0.012 mol) of ODPA was added together with 5 g of NMP, and the mixture was stirred at 60 ° C. for 4 hours. bottom. Then, the mixture was stirred at 180 ° C. for 4 hours, and after the stirring was completed, the solution was poured into 300 mL of water, and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-24).

10 g of the obtained resin (A-24), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A24 of the resin composition was obtained. Using the obtained varnish A24, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 25]
Under a dry nitrogen stream, 5.81 g (0.004 mol) of silsesquioxane structure-containing monomer (S-2) and 4.12 g (0.011 mol) of BAHF were dissolved in 20 g of NMP. To this, 3.16 g (0.015 mol) of TAC was added together with 13 g of NMP, and the mixture was stirred at 40 ° C. for 4 hours. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-25).

10 g of the obtained resin (A-25), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A25 of a resin composition was obtained. Using the obtained varnish A25, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 26]
Under a dry nitrogen stream, 5.81 g (0.004 mol) of silsesquioxane structure-containing monomer (S-2) and 4.12 g (0.011 mol) of BAHF were dissolved in 20 g of NMP. To this, 4.19 g (0.015 mol) of BPDC was added together with 16 g of NMP, and the mixture was stirred at 40 ° C. for 4 hours. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-26).

10 g of the obtained resin (A-26), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A26 was obtained. Using the obtained varnish A26, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 27]
A resin (A-27) was obtained by synthesizing in the same manner as in Example 1 except that DFA was not added.
10 g of the obtained resin (A-27), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A27 was obtained. Using the obtained varnish A27, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 28]
Under a yellow light, 0.6 g of NCI-831 was weighed, 35 g of MBA was added, and the mixture was stirred and dissolved. Next, 20 g of an MBA solution of 30% by mass of the resin (A-1) synthesized in the same manner as in Example 1 and 5 g of an MBA solution of 80% by mass of DPHA were added and stirred to obtain a mixed solution as a uniform solution. rice field. A varnish N1 of a negative photosensitive resin composition was obtained. Using the obtained varnish N1, the flatness evaluation and the pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Example 29]
Under a yellow light, 0.6 g of NCI-831 was weighed, 35 g of MBA was added, and the mixture was stirred and dissolved. Next, 20 g of an MBA solution of 30% by mass of the resin (A-24) synthesized in the same manner as in Example 17 and 5 g of an MBA solution of 80% by mass of DPHA were added and stirred to obtain a mixed solution as a uniform solution. rice field. A varnish N2 of a negative photosensitive resin composition was obtained. Using the obtained varnish N2, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 5.

[Comparative Example 1]
Under a dry nitrogen stream, 5.49 g (0.015 mol) of BAHF and 13.35 g (0.015 mol) of KF-8010 (manufactured by Shinetsu Silicone Co., Ltd.) were dissolved in 20 g of NMP. To this, 9.31 g (0.03 mol) of ODPA was added together with 25 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. Then, 7.2 g (0.06 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-28).

10 g of the obtained resin (A-28), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A28 was obtained. Using the obtained varnish A28, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 6.

[Comparative Example 2]
2.90 g (0.008 mol) of Bis-AT-AF was dissolved in 20 g of NMP under a dry nitrogen stream. To this, 11.86 g (0.008 mol) of the silsesquioxane structure-containing monomer (S-1) was added together with 20 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. Then, 1.9 g (0.016 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-29).

10 g of the obtained resin (A-29), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A29 of a resin composition was obtained. Using the obtained varnish A29, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 6.

[Comparative Example 3]
A resin (A-30) was obtained by synthesizing in the same manner as in Comparative Example 2 except that DFA was not added.
10 g of the obtained resin (A-30), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A varnish A30 of the resin composition was obtained. Using the obtained varnish A30, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 6.

[Comparative Example 4]
Under a dry nitrogen stream, 10.99 g (0.03 mol) of BAHF was dissolved in 50 g of NMP. To this, 9.31 g (0.03 mol) of ODPA was added together with 20 g of NMP, and the mixture was stirred at 40 ° C. for 8 hours. Then, 7.2 g (0.06 mol) of DFA was added, and stirring was continued at 40 ° C. for 1 hour. After completion of stirring, the solution was poured into 300 mL of water and the solid precipitate was collected by filtration. Further, the mixture was washed 3 times with 100 mL of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-31).

10 g of the obtained resin (A-31), 3.0 g of the quinone diazide compound (DQ-1) obtained in Synthesis Example 2, and 1.0 g of Nicarac MX-270 (E-1) were added to 50 g of GBL for positive photosensitive. A resin composition varnish A31 was obtained. Using the obtained varnish A31, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 6.

[Comparative Example 5]
Under a yellow light, 0.6 g of NCI-831 was weighed, 35 g of MBA was added, and the mixture was stirred and dissolved. Next, 20 g of an MBA solution of 30% by mass of the resin (A-28) synthesized in the same manner as in Comparative Example 1 and 5 g of an MBA solution of 80% by mass of DPHA were added and stirred to obtain a mixed solution as a uniform solution. rice field. A varnish N3 of a negative photosensitive resin composition was obtained. Using the obtained varnish N3, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 6.

[Comparative Example 6]
Under a yellow light, 0.6 g of NCI-831 was weighed, 35 g of MBA was added, and the mixture was stirred and dissolved. Next, 20 g of an MBA solution of 30% by mass of the resin (A-29) synthesized in the same manner as in Comparative Example 3 and 5 g of an MBA solution of 80% by mass of DPHA were added and stirred to obtain a mixed solution as a uniform solution. rice field. A varnish N4 of a negative photosensitive resin composition was obtained. Using the obtained varnish N4, flattening property evaluation and pattern dimensional stability evaluation were performed as described above. The evaluation results are shown in Table 6.

1: Step substrate 2: Hardened product

Claims (13)

One or more kinds of resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and two or more kinds of copolymers thereof, and the resin (A) is silsesqui. A resin (A) having an oxazole structure and having a weakly acidic group having an acid dissociation constant in dimethylsulfoxide of 13.0 or more and 23.0 or less at the main chain and / or the terminal of the resin (A). The resin (A) according to claim 1, wherein the weakly acidic group is at least one selected from the group consisting of a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group and a hexafluoroisopropyl alcohol group. The claim that the content of the weakly acidic group is 10 mol% or more and 500 mol% or less with respect to 100 mol% of the structural unit represented by the following general formula (1-3) in the resin (A). The resin (A) according to 1 or 2.

(In the general formula (1-3), R ¹ represents an organic group having 1 or more carbon atoms and 100 or less carbon atoms, which is bonded to a hydrogen atom, a halogen atom, or silicon with a carbon atom.) The resin (A) according to any one of claims 1 to 3, wherein the resin (A) has a residue derived from a diamine represented by the general formula (2).

(In the general formula (2), X ¹ represents a single bond, an ether bond, a sulfide bond, a disulfide bond, a sulfonyl group, or a divalent organic group having 1 to 200 carbon atoms. X ² and X ³ are. Each independently represents a single bond or a divalent organic group ^{having 1 or more and 200 or less carbon atoms. R 2} and R ³ independently represent a monovalent organic group having 1 or more and 200 or less carbon atoms, respectively. A ¹ and A. ² represents a weakly acidic group having an acid dissociation constant of 13.0 or more and 23.0 or less independently in dimethyl sulfoxide. A and b are independently integers of 0 or more and 4 or less, respectively, and c and d. Are independently integers of 0 or more and 4 or less, a + b ≧ 1, and 1 ≦ a + b + c + d ≦ 8. X ¹ , X ² , X ³ , R ² , R ³ , A ¹ , and A ² are , It may be different in each of a plurality of repeating units contained in the resin.) The invention according to any one of claims 1 to 3, wherein the resin (A) has a residue derived from at least one selected from the group consisting of diamines represented by the structural formulas (2A) to (2J). Resin (A).

The resin (A) according to any one of claims 1 to 5, wherein the silsesquioxane structure includes a cage-type silsesquioxane structure. A photosensitive resin composition containing the resin (A), the photosensitive compound (B) and the solvent (C) according to any one of claims 1 to 6. The photosensitive resin composition according to claim 7, wherein the photosensitive compound (B) contains a photoacid generator (b1). The photosensitive resin composition according to claim 7, wherein the photosensitive compound (B) contains a photopolymerization initiator (b2), and the photosensitive resin composition further contains a radically polymerizable compound (D). A cured product of the photosensitive resin composition according to any one of claims 7 to 9. An organic EL display device comprising the cured product according to claim 10. A semiconductor device comprising the cured product according to claim 10. A step of applying the photosensitive resin composition according to any one of claims 7 to 9 to a substrate to form a photosensitive resin film, a step of drying the photosensitive resin film, and a step of exposing the dried photosensitive resin film. A method for producing a cured product, which comprises a step of developing an exposed photosensitive resin film and a step of heat-treating the developed photosensitive resin film to obtain a cured product.

Images