Resin composition, cured product, and display device or semiconductor device

Abstract

This invention addresses the problem of obtaining a cured product which has excellent thinner solubility and in which contact resistance of an electrode after ashing is suppressed. The resin composition contains components (a) to (c), the component (a) having 1–80 (inclusive) mol% of a diamine residue represented by formula (1) with respect to 100 mol% of all diamine residues contained in the skeleton of the resin of the component (a). Component (a): at least one resin selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof Component (b): a photosensitizer Component (c): a solvent (In formula (1), each R1 to R8 independently represents a C1–C4 alkyl group or a hydrogen atom, and each X independently represents –CH2–, –C(CH3)2–, –O–, –S–, –SO2–, or a single bond. Each of p, q, r and s independently represents an integer of 0 or 1. * represents a bonded part.)

Description

Resin composition, cured product, and display device or semiconductor device

[0001] The present invention relates to a resin composition, more specifically to a resin composition suitable for use in a bank layer of an organic electroluminescence (hereinafter referred to as organic EL) display device, a planarization layer of a driving thin film transistor (hereinafter referred to as TFT) substrate of an organic EL display device, a surface protection layer, an interlayer insulating layer and / or a rewiring layer of a semiconductor device, a wiring protection insulating layer of a circuit board, an on-chip microlens of a solid-state imaging device, or a planarization layer for the solid-state imaging device, a cured product of the composition, and a display device or semiconductor device comprising the cured product.

[0002] Conventionally, photosensitive polyimides and / or photosensitive polybenzoxazoles, which have excellent heat resistance, electrical insulation properties, mechanical properties, etc. and can be patterned by photolithography, have been widely used for bank layers of organic EL display devices, planarizing layers of TFT substrates, surface protective films of semiconductor elements, and interlayer insulating films of electronic components, and many of these have been proposed (see, for example, Patent Documents 1 and 2).

[0003] The polyimide, polybenzoxazole, or precursor of either of them used in conventional photosensitive polyimides and / or photosensitive polybenzoxazoles generally has a fluorine-containing group such as a trifluoromethyl group in its resin structure, but has a problem in that fluorine-containing residues generated during dry etching adhere to the electrode in the opening, increasing the contact resistance of the electrode. In response to this problem, a method using a fluorine-free organic insulating film is disclosed, for example, in Patent Document 3.

[0004] On the other hand, Patent Document 4 discloses a polybenzoxazole precursor having a 5,5'-diamino-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane residue as a resin used in a positive-type photosensitive resin composition having excellent heat resistance, low dielectric properties, and high resolution, and Patent Document 5 discloses a polybenzoxazole precursor having a 6,6'-dicarboxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane residue as a resin used in a positive-type photosensitive resin composition that allows patterning with i-line, has high resolution, and causes little warpage of Si wafers after curing the resin.

[0005] Japanese Patent Application Laid-Open No. 2002-91343 Japanese Patent Application Laid-Open No. 2002-116715 Japanese Patent Application Laid-Open No. 2009-177113 Japanese Patent Application Laid-Open No. 2007-31511 Japanese Patent Application Laid-Open No. 2005-227654

[0006] However, conventional polyimides, polybenzoxazoles, and precursors thereof that do not have a fluorine-containing group such as a trifluoromethyl group have poor solubility in organic solvents, and although they are soluble in some aprotic polar solvents such as N-methyl-2-pyrrolidone and γ-butyrolactone, they have the problem of insufficient solubility in propylene glycol monomethyl ether, which is widely used as a thinner in photolithography processes. The resins disclosed in Patent Documents 3 to 5 have problems with at least one of solubility in propylene glycol monomethyl ether and contact resistance of electrodes after ashing of the cured product.

[0007] In order to solve the above problems, the present invention has the following configuration: [1] A resin composition containing the following components (a) to (c), wherein component (a) contains 1 mol % to 80 mol % of diamine residues represented by formula (1) relative to 100 mol % of all diamine residues contained in the resin skeleton of component (a): Component (a): at least one resin selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof; Component (b): a photosensitizer; and Component (c): a solvent.

[0008]

[0009] (In formula (1), R １ ~R ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and each X independently represents -CH ２ -, -C(CH ３ ) ２ -, -O-, -S-, -SO ２represents - or a single bond. p, q, r, and s each independently represent an integer of 0 or 1. * represents a bonding site.) [2] The resin composition according to [1], wherein the skeleton of the resin of component (a) further contains one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2) and dicarboxylic acid residues represented by formula (3).

[0010]

[0011] (In formulas (2) and (3), * represents a bonding site.) [3] The resin composition according to [1] or [2], wherein the skeleton of the resin of component (a) further contains a diamine residue represented by formula (4), and the resin composition contains 1 to 50 mol % of diamine residues represented by formula (1) and 50 to 95 mol % of diamine residues represented by formula (4) relative to 100 mol % of all diamine residues in the skeleton of the resin of component (a).

[0012]

[0013] (In formula (4), Y represents a divalent organic group having 1 to 20 carbon atoms, -O-, -S-, -SO ２ represents - or a single bond, R １１ and R １２ are each independently -CH ２ -, -C(CH ３ ) ２represents -, -O-, -NHC(=O)-, or -C(=O)NH-. Each t independently represents an integer of 0 or 1. However, formula (4) does not include the structure represented by formula (1). * represents a bonding site.) [4] The resin composition according to any of [1] to [3], wherein the component (a) is a polyimide precursor or a polyimide, and the content of the (I) amic acid structure is defined as u mol %, the content of the (II) amic acid ester structure is defined as v mol %, and the content of the (III) imide structure is defined as w mol %, relative to 100 mol % in total of the (I) amic acid structure, (II) amic acid ester structure, and (III) imide structure in the resin skeleton of the component (a), satisfies 0≦v≦80 and 10≦w≦80 (where u+v+w=100). [5] The resin composition according to any one of [1] to [4], wherein the photosensitizer of the component (b) contains (b1) a quinone diazide compound. [6] The resin composition according to any one of [1] to [5], wherein the photosensitizer of the component (b) contains (b2) a photopolymerization initiator and further contains (d) a compound having a polymerizable unsaturated bond group. [7] The resin composition according to any one of [1] to [6], further containing the following component (e), wherein the component (e) is contained in an amount of 10 to 50 parts by mass per 100 parts by mass of the component (a). Component (e): a compound having one or more groups selected from the group consisting of a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, and an isocyanate group [8] The resin composition according to any one of [1] to [7], wherein the component (a) does not contain a fluorine element and further contains the following component (f), wherein the component (f) is contained in an amount of 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the component (a). Component (f): a compound represented by formula (5):

[0014]

[0015] (In formula (5), R １３ ~R １５ each independently represents an alkyl group having 1 to 4 carbon atoms, R １６represents an alkylene group having 1 to 4 carbon atoms.) [9] A cured product obtained by curing the resin composition according to any one of [1] to [8].

[10] The cured product according to [9], having a fluorine content of 0 mass% or more and 0.5 mass% or less.

[11] A display device comprising the cured product according to [9] or

[10] .

[12] A semiconductor device comprising the cured product according to [9] or

[10] .

[0016] The resin composition of the present invention has excellent solubility in thinners and can give a cured product that reduces the contact resistance of electrodes after ashing.

[0017] 1 is a schematic diagram illustrating a procedure for producing an organic EL display device according to an example.

[0018] An embodiment of the present invention will now be described in detail.

[0019] The resin composition of the present invention contains the following components (a) to (c), in which component (a) contains 1 mol % to 80 mol % of diamine residues represented by formula (1) relative to 100 mol % of all diamine residues contained in the resin skeleton of component (a): Component (a): at least one resin selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof; Component (b): a photosensitizer; and Component (c): a solvent.

[0020]

[0021] (In formula (1), R １ ~R ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and each X independently represents -CH ２ -, -C(CH ３ ) ２ -, -O-, -S-, -SO ２ p, q, r, and s each independently represent an integer of 0 or 1. * represents a bonding site.) The resin composition of the present invention has excellent solubility in thinner, and it is possible to obtain a cured product that exhibits low contact resistance of electrodes after ashing.

[0022] Each component will be described below.

[0023] <Component (a): At Least One Resin Selected from the Group Consisting of Polyimide Precursor, Polyimide, Polybenzoxazole Precursor, Polybenzoxazole, and Copolymers Thereof> The component (a) used in the resin composition of the present invention is at least one resin selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor, polybenzoxazole, and copolymers thereof.

[0024] The polyimide precursor, polyimide, polybenzoxazole precursor, polybenzoxazole, and copolymers thereof preferably used as component (a) in the present invention can be synthesized by known methods. Examples of polyimide precursors include polyamic acids, polyamic acid esters, polyamic acid amides, and polyisoimides. Examples of polybenzoxazole precursors include polyhydroxyamides. Copolymers of at least two resins selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, and polybenzoxazoles can be synthesized by known methods.

[0025] The component (a) used in the resin composition of the present invention is characterized in that it contains 1 mol % or more and 80 mol % or less of diamine residues represented by formula (1) relative to 100 mol % of all diamine residues contained in the resin skeleton of component (a).

[0026] In the present invention, the diamine residues represented by formula (1) in component (a) play an important role, and by having 1 mol % to 80 mol % of diamine residues represented by formula (1) relative to 100 mol % of all diamine residues contained in the resin skeleton of component (a), it becomes possible to achieve both thinner solubility and suppression of electrode contact resistance after ashing of the cured product.

[0027] Preferred examples of the diamine residue represented by formula (1) include, but are not limited to, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane residue, 6,6'-diamino-3,3,3',3'-tetramethyl-1,1'-spirobiindane residue, 6,6'-bis(4-amino-3-hydroxyphenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane residue, and the like.

[0028] The amount of diamine residues represented by formula (1) relative to 100 mol% of all diamine residues contained in the skeleton of the resin of component (a) is, from the viewpoint of thinner solubility, 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, still more preferably 20 mol% or more, and particularly preferably 25 mol% or more, and from the viewpoint of sensitivity, it is 80 mol% or less, preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less.

[0029] The skeleton of the resin of component (a) in the present invention contains 20 mol % to 99 mol % of diamine residues different from the diamine residue represented by formula (1). Preferred examples of such diamine residues include 2,2-bis(3-amino-4-hydroxyphenyl)propane residue, bis(3-amino-4-hydroxyphenyl)sulfone residue, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane residue, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane residue, bis(3-amino-4-hydroxyphenyl)methylene residue, bis(3-amino-4-hydroxyphenyl)ether residue, 3,3'-diamino-4,4'-dihydroxyphenyl Sulfophenyl residue, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene residue, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane residue, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane residue, bis[3-(3-aminobenzamido)-4-hydroxyphenyl]sulfone residue, bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone residue, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]fluorene residue, phenyl]hexafluoropropane residue, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane residue, 1,1-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]cyclohexane residue, 1,1-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]cyclohexane residue, 9,9-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]fluorene residue, 9,9-bis[3-(4-aminobenzamido)-4-hydroxyphenyl] hydroxyl group-containing diamine residues such as 3-sulfonic acid-4,4'-diaminodiphenyl ether residue, sulfonic acid-containing diamine residues such as 3-sulfonic acid-4,4'-diaminodiphenyl ether residue, thiol group-containing diamine residues such as dimercaptophenylenediamine residue, 3,4'-diaminodiphenyl ether residue, 4,4'-diaminodiphenyl ether residue, 3,4'-diaminodiphenylmethane residue, 4,4'-diaminodiphenylmethane residue, 3,4'-diaminodiphenyl sulfone residue, 4,4'-diaminodiphenyl sulfone residue, 3,4'-diaminodiphenyl sulfide residue, 4,4'-diaminodiphenyl sulfide residue, 1,4-bis(4-aminophenoxy)benzene residue, benzine residue, m-phenylenediamine residue, p-phenylenediamine residue, 1,5-naphthalenediamine residue, 2,6-naphthalenediamine residue, bis(4-aminophenoxyphenyl)sulfone residue, bis(3-aminophenoxyphenyl)sulfone residue, bis(4-aminophenoxy)biphenyl residue, bis{4-(4-aminophenoxy)phenyl}ether residue, 1,4-bis(4- aminophenoxy)benzene residue, 2,2'-dimethyl-4,4'-diaminobiphenyl residue, 2,2'-diethyl-4,4'-diaminobiphenyl residue, 3,3'-dimethyl-4,4'-diaminobiphenyl residue, 3,3'-diethyl-4,4'-diaminobiphenyl residue, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl residue, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl residue, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl residue, 2,2'-bis(trifluoromethyl) aromatic diamine residues such as 1,3-bis(3-aminopropanol)-4,4'-diaminodiphenyl ether residues, diamine residues in which some of the hydrogen atoms of these aromatic rings have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like, diamine residues having a nitrogen-containing heteroaromatic ring such as 2,4-diamino-1,3,5-triazine (guanamine) residue, 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanamine) residue, and 2,4-diamino-6-phenyl-1,3,5-triazine (benzoguanamine) residue, Examples of the diamine include silicone diamine residues such as 1,3-bis(p-aminophenyl)-1,1,3,3-tetramethyldisiloxane residue, 1,3-bis(p-aminophenethyl)-1,1,3,3-tetramethyldisiloxane residue, and 1,7-bis(p-aminophenyl)-1,1,3,3,5,5,7,7-octamethyltetrasiloxane residue, and alicyclic diamine residues such as cyclohexyldiamine residue and methylenebiscyclohexylamine residue, but are not limited to these.

[0030] The skeleton of the resin of component (a) in the present invention further contains a diamine residue represented by formula (4), and it is preferable that the skeleton of the resin of component (a) contains 1 to 50 mol % of diamine residues represented by formula (1) and 50 to 95 mol % of diamine residues represented by formula (4) relative to 100 mol % of all diamine residues contained in the skeleton of the resin of component (a). Such a design is preferable because it makes it easier to achieve both thinner solubility and high sensitivity.

[0031]

[0032] (In formula (4), Y represents a divalent organic group having 1 to 20 carbon atoms, -O-, -S-, -SO ２ represents - or a single bond, R １１ and R １２ are each independently -CH ２ -, -C(CH ３ ) ２represents -, -O-, -NHC(=O)-, or -C(=O)NH-. t represents an integer of 0 or 1. However, formula (4) does not include the structure represented by formula (1). * represents a bond. Examples of the diamine residue represented by formula (4) include the above-mentioned 2,2-bis(3-amino-4-hydroxyphenyl)propane residue, bis(3-amino-4-hydroxyphenyl)sulfone residue, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane residue, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane residue, bis(3-amino-4-hydroxyphenyl)methylene residue, bis(3-amino-4-hydroxyphenyl)ether residue, 3,3'-diamino-4,4'-dihydroxybiphenyl residue, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene residue, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane residue, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane residue, bis[3-(3 ... Examples of hydroxyl group-containing diamine residues include, but are not limited to, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]sulfone residue, bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone residue, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane residue, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane residue, 1,1-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]cyclohexane residue, 1,1-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]cyclohexane residue, 9,9-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]fluorene residue, and 9,9-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]fluorene residue.Among these, 2,2-bis(3-amino-4-hydroxyphenyl)propane residue, bis(3-amino-4-hydroxyphenyl)sulfone residue, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane residue, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene residue, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane residue, bis[3-(3-aminobenzamido)-4-hydroxyphenyl]sulfone residue, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane residue, 1,1-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]cyclohexane residue, and 9,9-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]fluorene residue are preferably used.

[0033] The content of the diamine residue represented by formula (4) contained in the skeleton of the resin of component (a) in the present invention is preferably 50 mol % or more, more preferably 55 mol % or more, even more preferably 60 mol % or more, still more preferably 65 mol % or more, and particularly preferably 70 mol % or more, relative to 100 mol % of all diamine residues contained in the skeleton of the resin of component (a), from the viewpoint of appropriately increasing the alkali solubility of component (a); and is 95 mol % or less, preferably 90 mol % or less, more preferably 85 mol % or less, and particularly preferably 80 mol % or less, from the viewpoint of appropriately decreasing the alkali solubility of component (a).

[0034] The skeleton of the resin of component (a) in the present invention preferably contains a tetracarboxylic acid residue and / or a dicarboxylic acid residue.

[0035] Preferable examples of the tetracarboxylic acid residue contained in the skeleton of the resin of component (a) in the present invention include a pyromellitic acid residue, a 3,3',4,4'-biphenyltetracarboxylic acid residue, a 2,3,3',4'-biphenyltetracarboxylic acid residue, a 2,2',3,3'-biphenyltetracarboxylic acid residue, a 3,3',4,4'-benzophenonetetracarboxylic acid residue, a 2,2',3,3'-benzophenonetetracarboxylic acid residue, a 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane residue, a 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane residue, a 1,1-bis(3,4-dicarboxyphenyl)ethane residue, a 1,1-bis(2,3-dicarboxyphenyl)ethane residue, a bis(3,4-dicarboxyphenyl)methane residue, a bis(2,3-dicarboxyphenyl)methane residue, a bis(3,4-dicarboxyphenyl)sulfone residue, a bis(3 ,4-dicarboxyphenyl) ether residue, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane residue, 1,2,5,6-naphthalenetetracarboxylic acid residue, 2,3,6,7-naphthalenetetracarboxylic acid residue, 2,3,5,6-pyridinetetracarboxylic acid residue, 3,4,9,10-perylenetetracarboxylic acid residue, and the like; and aliphatic tetracarboxylic acid residues such as butanetetracarboxylic acid residue, 1,2,3,4-cyclobutanetetracarboxylic acid residue, 1,2,3,4-cyclopentanetetracarboxylic acid residue, 1,2,4,5-cyclohexanetetracarboxylic acid residue, 2,2-bis(3,4-dicarboxycyclohexyl)propane residue, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid residue, and the like.

[0036] Preferred examples of the dicarboxylic acid residue contained in the skeleton of the resin of component (a) in the present invention include, but are not limited to, terephthalic acid residue, isophthalic acid residue, diphenylether-4,4'-dicarboxylic acid residue, bis(4-carboxyphenyl)hexafluoropropane residue, 4,4'-biphenyldicarboxylic acid residue, and benzophenone-4,4'-dicarboxylic acid residue.

[0037] The skeleton of the resin component (a) in the present invention preferably contains one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2) and dicarboxylic acid residues represented by formula (3). This design is preferred because it facilitates achieving both thinner solubility and high sensitivity. Polyimide precursors and / or polyimides having tetracarboxylic acid residues represented by formula (2), and polybenzoxazole precursors having dicarboxylic acid residues represented by formula (3), are preferred because they facilitate achieving both high sensitivity and thinner solubility. Among the group consisting of tetracarboxylic acid residues represented by formula (2) and dicarboxylic acid residues represented by formula (3), from the viewpoint of heat resistance of the film-like cured product (hereinafter referred to as the cured film), the skeleton of the resin component (a) preferably contains one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2-a). Furthermore, from the viewpoint of transparency of the cured film, the skeleton of the resin component (a) preferably contains one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2-b).

[0038]

[0039] (In formulas (2-a) and (2-b), * represents a bonding site.) Furthermore, from the viewpoint of achieving both heat resistance and transparency of the cured film, it is preferable that the skeleton of the resin of component (a) contains one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2-a) and one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2-b). When the component (a) is a polyimide precursor or a polyimide, the content of the tetracarboxylic acid residues represented by formula (2-a) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to 100 mol% of all tetracarboxylic acid residues contained in the resin skeleton of the component (a). The content of the tetracarboxylic acid residues represented by formula (2-b) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more. The total content of the tetracarboxylic acid residues represented by formula (2-a) and the tetracarboxylic acid residues represented by formula (2-b) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol%.

[0040] The component (a) is preferably alkali-soluble. When the component (a) is alkali-soluble, it can be made into an alkali-developable photosensitive resin composition.

[0041] In order to impart alkali solubility to the component (a), it is preferable that the component (a) has a phenolic hydroxyl group in its structural unit. From the viewpoint of imparting alkali solubility, the amount of the phenolic hydroxyl group introduced into the component (a) is preferably 1.0 mol / kg or more, more preferably 1.5 mol / kg or more, even more preferably 2.0 mol / kg or more, and particularly preferably 2.2 mol / kg or more, and from the viewpoint of the chemical resistance of the cured film, it is preferably 5.0 mol / kg or less, more preferably 4.0 mol / kg or less, even more preferably 3.5 mol / kg or less, and particularly preferably 3.2 mol / kg or less.

[0042] In the present invention, alkali-soluble refers to a dissolution rate of 50 nm / min or more, determined from the reduction in film thickness when a solution of a resin dissolved in γ-butyrolactone is applied to a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsed with pure water.

[0043] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to cap the main chain ends of component (a) with a known end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. For the purpose of improving the chemical resistance of the cured resin film obtained by heat curing, a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound having at least one alkenyl group or alkynyl group can also be used as the end-capping agent.

[0044] The component (a) in the present invention is a polyimide precursor or polyimide, and when the content of the (I) amic acid structure, the (II) amic acid ester structure, and the (III) imide structure in the resin skeleton of the component (a) is defined as u mol %, the content of the (II) amic acid ester structure as v mol %, and the content of the (III) imide structure as w mol %, relative to the total of 100 mol % of the (I) amic acid structure, (II) amic acid ester structure, and (III) imide structure, it is preferable to satisfy the following: 0≦v≦80 and 10≦w≦80 (where u+v+w=100). Such a design is preferable because it makes it easy to achieve both thinner solubility and high sensitivity.

[0045] In the present invention, (I) an amic acid structure, (II) an amic acid ester structure, and (III) an imide structure refer to structures each having the partial structure shown below as a minimum unit.

[0046]

[0047] (In (I), (II), and (III), C ａ and C ｂ are two carbon atoms adjacent to each other via a covalent bond, and C ａ and C ｂThe covalent bond between C is a single bond or a double bond, ａ and C ｂ may be part of an aliphatic cyclic structure or an aromatic cyclic structure. １７ represents a monovalent organic group having 1 to 10 carbon atoms. * represents a bonding site.) (II) The content v mol % of the amic acid ester structure is preferably 0 mol % or more, more preferably 10 mol % or more, even more preferably 20 mol % or more, and particularly preferably 30 mol % or more, from the viewpoint of frozen storage stability, and is preferably 80 mol % or less, more preferably 75 mol % or less, even more preferably 70 mol % or less, and particularly preferably 65 mol % or less, from the viewpoint of reducing film shrinkage during curing.

[0048] From the viewpoint of reducing film shrinkage during curing, the content w mol% of the (III) imide structure is preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, and particularly preferably 25 mol% or more. From the viewpoint of increasing the sensitivity of the resin composition, it is preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and particularly preferably 50 mol% or less. In the present invention, a polyimide precursor or polyimide having a (III) imide structure content w mol% of 0 mol% or more and 80 mol% or less is defined as a polyimide precursor, and a polyimide having a content w mol% of more than 80 mol% and 100 mol% or less is defined as a polyimide. In addition, in the present invention, a polyimide precursor having a (II) amic acid ester structure content v mol% of 0 mol% or more and less than 10 mol% is defined as a polyamic acid, and a polyamic acid ester having a content v mol% of 10 mol% or more and 100 mol% or less is defined as a polyamic acid.

[0049] The content (v mol %) of the above (II) amic acid ester structure can be determined, for example, by the following method. First, the component (a) is dissolved in deuterated dimethyl sulfoxide (DMSO-d ６ ) and １ H NMR is measured. The content v mol % of the amic acid ester structure can be calculated from the area ratio between the peak derived from the protons of the resin skeleton and the peak derived from the protons of the carboxylic acid ester.

[0050] The content (w mol %) of the imide structure (III) can be determined, for example, by the following method. First, the infrared absorption spectrum of the component (a) is measured, and the absorption peak (1,780 cm ) of the imide structure due to polyimide is detected. －１ Near 1,377 cm －１ The presence of an absorption peak (around 1,470 cm) due to an aromatic ring was confirmed. －１ When the peak intensity at 1,377 cm －１ Next, the component (a) is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured to determine the absorption peak (1,470 cm) due to the aromatic ring. －１ When the peak intensity at 1,377 cm －１ The peak intensity (Z) around the peak is measured. The ratio of these peak intensities corresponds to the content w (mol %) of the imide structure in the resin skeleton of component (a) before heat treatment (w = Y / Z × 100 (mol %)).

[0051] The content (u mol %) of the above-mentioned (I) amic acid structure in the present invention can be calculated by the following formula.

[0052] The weight average molecular weight of component (a) can be determined in polystyrene equivalent terms by gel permeation chromatography (GPC), and from the viewpoint of folding endurance of the cured film, it is preferably more than 15,000, more preferably more than 18,000, even more preferably more than 20,000, and particularly preferably more than 25,000; and from the viewpoint of alkali solubility, it is preferably 40,000 or less, more preferably 38,000 or less, even more preferably 35,000 or less, and particularly preferably 30,000 or less.

[0053] It is more preferable that component (a) be obtained by precipitating the polymer in a poor solvent such as methanol or water after polymerization, followed by washing and drying. This allows the removal of low-molecular-weight components from the polymer, and significantly improves the folding endurance of the resin composition after heat curing.

[0054] The resin of component (a) in the present invention preferably does not contain fluorine element. By not containing fluorine element in component (a), when the resin composition is cured, it is possible to reduce the contact resistance of the electrode after ashing. The resin of component (a) that does not contain fluorine element can be obtained by synthesis using only monomers that do not contain fluorine element.

[0055] <Component (b): Photosensitizer> The resin composition of the present invention contains a photosensitizer as component (b). By containing a photosensitizer as component (b), photosensitivity can be imparted to the resin composition. Examples of photosensitizers used as component (b) include photoacid generators and photopolymerization initiators. Photoacid generators are compounds that generate acid upon irradiation with light, and examples include quinone diazide compounds and onium salt compounds. Photopolymerization initiators are compounds that undergo bond cleavage and / or reaction upon exposure to generate radicals.

[0056] In the resin composition of the present invention, the photosensitizer (b) preferably contains a quinone diazide compound (b1) as a photoacid generator. By containing the quinone diazide compound (b1), acid is generated in the light-irradiated areas, increasing the solubility of the light-irradiated areas in an alkaline aqueous solution, thereby forming a positive relief pattern in which the light-irradiated areas dissolve.

[0057] (b1) The quinone diazide compound is preferably a compound in which the sulfonic acid of naphthoquinone diazide sulfonic acid is bonded to a compound having a phenolic hydroxyl group via an ester bond. Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, and BisP-OC. HP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X , DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, T ML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol Examples of suitable quinone diazide compounds for use in the present invention include compounds such as phenol E, methylene bisphenol, BisP-AP (all trade names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, and TM-BIP-A (all trade names, Asahi Organic Chemicals Co., Ltd.). Suitable examples of the quinone diazide compound for use in the present invention include compounds in which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced via an ester bond into any of these compounds having a phenolic hydroxyl group, but other compounds can also be used.

[0058] 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending into the g-line region of a mercury lamp and are suitable for g-line exposure. In the present invention, either 4-naphthoquinone diazide sulfonyl ester compounds or 5-naphthoquinone diazide sulfonyl ester compounds can be preferably used, but it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. It is also possible to obtain naphthoquinone diazide sulfonyl ester compounds containing both 4-naphthoquinone diazide sulfonyl groups and 5-naphthoquinone diazide sulfonyl groups in the same molecule, or a mixture of 4-naphthoquinone diazide sulfonyl ester compounds and 5-naphthoquinone diazide sulfonyl ester compounds can be used.

[0059] The naphthoquinone diazide sulfonyl ester compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid compound, and can be synthesized by a known method.

[0060] In the present invention, the content of the quinone diazide compound (b1) is preferably 0.01 to 50 parts by mass per 100 parts by mass of the component (a). From the viewpoint of pattern formation, the content of the quinone diazide compound (b1) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, and from the viewpoint of maintaining heat resistance, the content is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less.

[0061] The resin composition of the present invention preferably contains a (b2) photopolymerization initiator as the (b) component photosensitizer, and further contains a (d) compound having a polymerizable unsaturated bond group. Known photopolymerization initiators can be used as the (b2) photopolymerization initiator. Furthermore, two or more types of (b2) photopolymerization initiators may be contained.

[0062] The content of the (b2) photopolymerization initiator, relative to 100 parts by mass of the component (a), is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, from the viewpoint of folding endurance of the cured film; and from the viewpoint of maintaining heat resistance, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

[0063] <Component (c): Solvent> The resin composition of the present invention contains a solvent as component (c). Preferred examples of the solvent used as component (c) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such as tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate; alcohols such as diacetone alcohol and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

[0064] The content of component (c) is preferably 70 parts by mass or more, more preferably 100 parts by mass or more, per 100 parts by mass of component (a) from the viewpoint of resin dissolution, and is preferably 2,500 parts by mass or less, more preferably 2,000 parts by mass or less, from the viewpoint of obtaining an appropriate film thickness. In the present invention, even if a component is liquid at room temperature, a component present in the resin composition in an amount of less than 5 parts by mass per 100 parts by mass of component (a) is not considered to be a solvent.

[0065] <Component (d): Compound Having a Polymerizable Unsaturated Bond Group> The resin composition of the present invention preferably contains a compound having a polymerizable unsaturated bond group as the component (d).

[0066] By containing the aforementioned (b2) photopolymerization initiator and the (d) compound having a polymerizable unsaturated bond group, a radical crosslinking reaction occurs in the light-irradiated area, making the composition insoluble in an alkaline or organic developer, thereby obtaining a negative relief pattern.

[0067] Examples of the polymerizable unsaturated bond group contained in the compound having a polymerizable unsaturated bond group of component (d) include unsaturated double bond groups such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups, and unsaturated triple bond groups such as propargyl groups. Two or more of these may be contained. Among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred in terms of polymerizability. Furthermore, from the viewpoint of stability, it is preferable that one to four of these groups having an unsaturated bond be contained per molecule.

[0068] As the component (d), a known compound having a polymerizable unsaturated bond group can be used. Two or more types of component (d) may be contained.

[0069] The amount of the component (d) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of the component (a), from the viewpoint of the folding endurance of the cured film; and is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less, from the viewpoint of maintaining heat resistance.

[0070] <Component (e): Compound Having One or More Groups Selected from the Group Consisting of Methylol Group, Alkoxymethyl Group, Epoxy Group, Oxetanyl Group, and Isocyanate Group> The resin composition of the present invention preferably contains, as component (e), a compound having one or more groups selected from the group consisting of a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, and an isocyanate group. Furthermore, the resin composition of the present invention preferably contains component (e), and the component (e) is preferably contained in an amount of 10 to 50 parts by mass per 100 parts by mass of component (a). Component (e) is a compound that reacts with other molecules by heat to form chemical bonds and can be used as a thermal crosslinking agent. Component (e) crosslinks component (a) or other additive components, thereby enhancing the chemical resistance and hardness of the cured film after heat curing.

[0071] Preferred examples of the compound having a methylol group or an alkoxymethyl group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, and DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) Examples of suitable acrylic resins include MX-290, "NIKALAC" (registered trademark) MX-280, "NIKALAC" (registered trademark) MX-270, "NIKALAC" (registered trademark) MX-279, "NIKALAC" (registered trademark) MW-100LM, and "NIKALAC" (registered trademark) MX-750LM (all of which are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0072] Preferred examples of compounds having an epoxy group include, for example, "Epolite" (registered trademark) 40E, "Epolite" (registered trademark) 100E, "Epolite" (registered trademark) 200E, "Epolite" (registered trademark) 400E, "Epolite" (registered trademark) 70P, "Epolite" (registered trademark) 200P, "Epolite" (registered trademark) 400P, "Epolite" (registered trademark) 1500NP, "Epolite" (registered trademark) 80MF, "Epolite" (registered trademark) "Showfree" (registered trademark) CDMDG, "Showfree" (registered trademark) PETG, "Showfree" (registered trademark) BATG (all manufactured by Showa Denko K.K.), "Denacol" (registered trademark) EX-212L, "Denacol" (registered trademark) EX-214L, "Denacol" (registered trademark) EX-216L, "Denacol" (registered trademark) EX -321L, "Denacol" (registered trademark) EX-850L (all manufactured by Nagase ChemteX Corporation), "Epicoat" (registered trademark) 828, "Epicoat" (registered trademark) 1002, "Epicoat" (registered trademark) 1750, "Epicoat" (registered trademark) 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resins Co., Ltd.), "Epiclon" (registered trademark) EXA-9583, HP4032 , HP7300, N695 (all manufactured by DIC Corporation), VG3101L (manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark)-S, "TEPIC" (registered trademark)-G, "TEPIC" (registered trademark)-L (all manufactured by Nissan Chemical Industries, Ltd.), "Epotohto" (registered trademark) YH-434L (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPPN502H, NC3000, NC6000, GAN, GOT (all manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0073] Preferred examples of compounds having an oxetanyl group include, for example, "Ethanacol" (registered trademark) EHO, "Ethanacol" (registered trademark) OXBP, "Ethanacol" (registered trademark) OXTP, "Ethanacol" (registered trademark) OXMA (all manufactured by Ube Industries, Ltd.), oxetanized phenol novolak, etc.

[0074] Preferred examples of the compound having an isocyanate group include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, and diphenylmethane-4,4'-diisocyanate. o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, methylenebis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene d-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, and hydrogenated 1,4-xylylene diisocyanate.

[0075] Two or more types of component (e) may be used in combination. The content of component (e) is, relative to 100 parts by mass of component (a), preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, from the viewpoint of folding endurance of the cured film, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less, from the viewpoint of maintaining heat resistance.

[0076] <Component (f): Compound represented by formula (5)> The resin composition of the present invention preferably contains 0.01 parts by mass or more and 5 parts by mass or less of a compound represented by formula (5) as component (f) per 100 parts by mass of component (a).

[0077]

[0078] (In formula (5), R１３ ~R １５ each independently represents an alkyl group having 1 to 4 carbon atoms, R １６ represents an alkylene group having 1 to 4 carbon atoms.) By including component (f), the resin composition of the present invention can improve the storage stability of the resin composition during frozen storage. Preferred examples of component (f) include, but are not limited to, 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, and 3-n-butoxy-N,N-dimethylpropionamide.

[0079] The content of the (f) component is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the (a) component, from the viewpoint of storage stability during frozen storage; and from the viewpoint of increasing sensitivity, it is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.

[0080] In the resin composition of the present invention, the resin of component (a) preferably does not contain elemental fluorine, and the resin of component (f) preferably contains 0.01 to 5 parts by mass of a compound represented by formula (5) per 100 parts by mass of component (a). As described above, the absence of elemental fluorine in component (a) makes it possible to reduce the contact resistance of electrodes after ashing when the cured product is formed, and the inclusion of component (f) makes it possible to achieve both storage stability during frozen storage.

[0081] In addition to the components (a), (b), and (c), the resin composition of the present invention may contain, as necessary, components (d), (e), and (f), an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, and a colorant.

[0082] Next, a method for producing the resin composition of the present invention will be described. For example, a resin composition can be obtained by mixing and dissolving the components (a), (b), and (c) with, as needed, components (d), (e), and (f), an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, a colorant, and the like. Examples of dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is typically between room temperature and 80°C. The order in which the components are dissolved is not particularly limited; for example, a method in which the least soluble compounds are dissolved sequentially can be used.

[0083] The obtained resin composition is preferably filtered using a filter to remove dust and particles. The filter pore size may be, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, or 0.02 μm, but is not limited thereto. The filter material may be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), with polyethylene or nylon being preferred.

[0084] Next, the cured product of the present invention is obtained by curing the above-mentioned resin composition. In the present invention, curing refers to a state in which the resin composition does not exhibit fluidity even at 300°C or higher due to, for example, rigidification of the main chain skeleton or formation of a crosslinked structure due to the formation of imide rings or oxazole rings in component (a) contained in the resin composition of the present invention, formation of a crosslinked structure between component (d) and component (a) in addition to the above when component (d) is contained in the resin composition of the present invention, or formation of a crosslinked structure derived from component (e) in addition to the above when component (e) is contained in the resin composition.

[0085] A method for producing a cured product from the resin composition will be described. More specifically, the resin composition is applied to a substrate to form a resin film, the resin film is dried, and if necessary, the resin film is exposed to light, and the resin film is heat-cured to produce a cured product.

[0086] First, a resin composition is applied to a substrate to form a resin film. The process of applying a resin composition to a substrate to form a resin film is referred to as the coating process. Examples of coating methods include spin coating, slit coating, dip coating, spray coating, and printing. Among these, slit coating is preferred because it allows coating with a small amount of coating liquid and is advantageous in reducing costs. The amount of coating liquid required for slit coating is, for example, about 1 / 5 to 1 / 10 of that required for spin coating. Examples of slit coaters used for coating include the "Linear Coater" (registered trademark) manufactured by SCREEN Finetech Solutions Co., Ltd., the "Spinless" (registered trademark) manufactured by Tokyo Ohka Kogyo Co., Ltd., the "TS Coater" manufactured by Toray Engineering Co., Ltd., the "Table Coater" (registered trademark) manufactured by Chugai Ro Kogyo Co., Ltd., the "CS Series" and "CL Series" manufactured by Tokyo Electron Limited, the "In-line Slit Coater" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC Series" manufactured by Hirata Corporation. When using a slit coater, the coating speed is preferably in the range of 10 mm / sec to 400 mm / sec. The thickness of the resin film varies depending on the solids concentration and viscosity of the 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.

[0087] The substrate may be, but is not limited to, glass, silicon, ceramics, gallium arsenide, or other wafer, or a substrate having metal formed thereon as an electrode or wiring.

[0088] Next, the resin film on the substrate is dried. The process of drying the resin film on the substrate is referred to as the drying process. Known drying methods can be used, such as methods using a hot plate, an oven, or infrared rays. Alternatively, the substrate on which the resin film has been formed may be dried under reduced pressure. The heating temperature and heating time vary depending on the type and purpose of the resin film, but a heating temperature of 50°C to 180°C and a heating time of 1 minute to several hours are preferred.

[0089] If necessary, the dried resin film is exposed to actinic rays. The process of exposing the dried resin film is referred to as the exposure process. In particular, exposure is preferable for negative resin compositions because it promotes a photocrosslinking reaction. Actinic rays used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp are preferably used.

[0090] By heat-curing the dried resin film, a cured film, which is a film-like cured product, can be obtained. The process of heat-curing the resin film is referred to as a heat treatment process. During heat-curing, components with low heat resistance can be removed by volatilization, so this process can further improve heat resistance and chemical resistance. The heat-curing temperature is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 230°C or higher, from the viewpoint of improving the heat resistance of the cured film. From the viewpoint of improving the film toughness of the cured film, it is preferably 400°C or lower, more preferably 350°C or lower, even more preferably 300°C or lower, and particularly preferably 280°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat-curing time is preferably 30 minutes or longer, from the viewpoint of improving the heat resistance of the cured film. Furthermore, it is preferably 3 hours or shorter, from the viewpoint of improving the film toughness of the cured film. For example, there may be mentioned a method of performing heat treatment at 150° C. and 260° C. for 60 minutes each, or a method of performing heat treatment while linearly increasing the temperature from room temperature to 270° C. over 2 hours.

[0091] The cured product of the present invention preferably has a fluorine element content of 0% by mass or more and 0.5% by mass or less. By keeping the fluorine element content low, it is possible to reduce the contact resistance of the electrode after ashing of the cured product. From the viewpoint of reducing the contact resistance of the electrode after ashing, the fluorine element content of the cured product of the present invention is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0% by mass.

[0092] Next, a method for producing a patterned cured product from the resin composition of the present invention will be described. More specifically, a patterned cured product can be produced by applying the resin composition to a substrate to form a resin film, drying the resin film, exposing the dried resin film, developing the exposed resin film, and heat-curing the developed resin film. In the method for producing a patterned cured product from the resin composition, the process of applying the resin composition to a substrate to form a resin film will be referred to as the coating process, the process of drying the resin film will be referred to as the drying process, the process of exposing the dried resin film will be referred to as the exposure process, the process of developing the exposed resin film will be referred to as the development process, and the process of heat-curing the developed resin film will be referred to as the heat treatment process. The coating process, drying process, and heat treatment process are the same as in the method for producing a cured product from the resin composition described above. Therefore, the resin film exposure process and development process will be described below.

[0093] As described above, the resin composition is applied to a substrate to form a resin film, and the resin film is dried and then exposed to actinic radiation through a mask having a desired pattern, followed by development, whereby the desired pattern can be formed.

[0094] Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the film has positive photosensitivity, the exposed area dissolves in a developer. When the film has negative photosensitivity, the exposed area hardens and becomes insoluble in a developer.

[0095] Next, the exposed resin film is developed. In the case of a positive type, the desired pattern is formed by removing the exposed areas with a developer. In the case of a negative type, the desired pattern is formed by removing the unexposed areas with a developer. As the developer, an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine is preferred. To these alkaline aqueous solutions, one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc., alcohols such as methanol, ethanol, isopropanol, etc., esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc., ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc., may be added. Development methods include spray, paddle, immersion, ultrasonic, etc.

[0096] Next, the pattern formed by development is preferably rinsed with pure water. Rinsing may be performed by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to pure water. Subsequently, the patterned cured product can be produced by the above-mentioned heat treatment step.

[0097] The resin composition of the present invention is suitably used for bank layers of organic EL display devices, planarizing layers of TFT substrates for driving organic EL display devices, wiring protection insulating layers of circuit boards, surface protection layers, interlayer insulating layers, and / or rewiring layers of semiconductor devices, on-chip microlenses of solid-state imaging devices, and planarizing layers for various displays and solid-state imaging devices.

[0098] The display device or semiconductor device of the present invention comprises the above-described cured product.

[0099] In the display device of the present invention, the bank layer and / or the planarization layer of the TFT substrate are made of the cured product of the present invention, and in the semiconductor device of the present invention, the surface protection layer, the interlayer insulating layer, and / or the rewiring layer are made of the cured product of the present invention. The cured product of the present invention can reduce the contact resistance of the electrodes after ashing, thereby providing a display device or semiconductor device with stable driving performance.

[0100] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods used in each example and comparative example will be described. Note that these evaluation methods are evaluations with n=1.

[0101] [Evaluation Method] (1) Content (v mol %) of (II) amic acid ester structure in resin Using a nuclear magnetic resonance (NMR) device (EX-270 manufactured by JEOL Ltd.), 10 mg of a resin containing an amic acid ester structure was dissolved in deuterated dimethyl sulfoxide (DMSO-d ６ ) in 0.8 g, and the solution １ H NMR was measured, and the content of the amic acid ester structure was calculated from the area ratio of the peak derived from the protons of the resin skeleton to the peak derived from the protons of the carboxylic acid ester. Note that resins not containing an amic acid ester structure were excluded from the evaluation.

[0102] (2) Resin (III) Imide Structure Content (w mol%) A resin having an imide or imide precursor structure was dissolved in γ-butyrolactone (hereinafter, GBL) at 35% by mass, and applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Co., Ltd.). The wafer was then baked on a hot plate at 120°C for 3 minutes to produce a resin film with a thickness of 4 to 5 μm. This wafer with the resin film was divided into two, and one half was heated and cured in a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 20 ppm or less) at 140°C for 30 minutes, and then further heated to 320°C for 1 hour. The transmission infrared absorption spectra of the resin film before and after heat curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak (1,780 cm) of the imide structure due to polyimide was observed.－１ Near 1,377 cm －１ After confirming the presence of an absorption peak (around 1,470 cm) due to an aromatic ring, －１ When the peak intensity at 1,377 cm －１ The peak intensities around the peaks (before heat curing: Y, after heat curing: Z) were determined. The content of imide structures in the resin before heat treatment was calculated from the ratio of these peak intensities (w = Y / Z x 100(%)). Note that resins not containing imide structures were excluded from the evaluation.

[0103] (3) Content of component (f) in resin composition The resin compositions of each example and comparative example were subjected to GC-MS analysis using a GC-MS device (manufactured by Agilent) under the following conditions: column temperature: 40 to 300°C, carrier gas: helium (1.5 mL / min). A calibration curve for component (f) was created to measure the content of component (f).

[0104] (4) Film Thickness The film thickness of the resin film on the support substrate was measured using an optical interference film thickness measuring device (Lambda Ace VM-1030 manufactured by SCREEN Holdings Co., Ltd.) The refractive index was measured at 1.629.

[0105] (5) Thinner Solubility The resin composition of each example and comparative example was applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 2 minutes to produce a resin film with a thickness of 2 μm. This wafer with resin film was divided into two, and one was immersed in 100 g of propylene glycol monomethyl ether (hereinafter, PGME) at 23°C for 2 minutes and rinsed with pure water. The other divided wafer with resin film was similarly immersed in 100 g of PGME at 23°C for 5 minutes and rinsed with pure water. Dissolution of the resin film was confirmed visually and by measuring the film thickness. Samples that were completely dissolved after 2 minutes of static immersion were judged to have good thinner solubility (3 points), samples that were not completely dissolved after 2 minutes of static immersion but were completely dissolved after 5 minutes of static immersion were judged to have insufficient thinner solubility (2 points), and samples that were not completely dissolved even after 5 minutes of static immersion were judged to have poor thinner solubility (1 point). Samples that were 3 points or higher were judged to have passed.

[0106] (6) Contact Resistance A schematic diagram of the fabrication procedure for a contact resistance evaluation board is shown in Figure 1. Note that in the schematic diagram, the sizes of the components are exaggerated or reduced for the sake of convenience.

[0107] First, a 100 nm ITO (indium tin oxide, transparent conductive film) was formed on the entire surface of a 38 mm x 46 mm alkali-free glass substrate (reference numeral 1) by sputtering, and then etched to form an auxiliary electrode (reference numeral 3) for connecting the first electrode (reference numeral 2) and the second electrode. The resulting substrate was ultrasonically cleaned for 10 minutes using Semicoclean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then washed with ultrapure water (Figure 1 (1)). Next, a predetermined resin composition described below was applied to the entire surface of the substrate by spin coating and prebaked on a hot plate at 120 °C for 2 minutes. The substrate was then exposed to UV light through a photomask using a mask aligner PEM-6M (manufactured by Union Optical Co., Ltd.) to dissolve the openings and the periphery of the substrate. The substrate was then developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), dissolving the unnecessary portions, and then rinsed with pure water. This substrate was heated and cured for 1 hour at a predetermined temperature in a nitrogen stream (oxygen concentration 20 ppm by volume or less) using a clean oven CLH-21CD-S. Four 2 mm square substrate effective areas (reference numeral 5) within the substrate were filled with rectangular openings (260 μm long and 70 μm wide) arranged at a vertical pitch of 465 μm and a horizontal pitch of 155 μm, each exposing a first electrode. The thickness of the cured resin was adjusted to approximately 1.0 μm (Figure 1 (2)). Next, the contact resistance evaluation substrate was subjected to argon plasma ashing using a plasma cleaning device SPC-100B+H (manufactured by Hitachi High-Tech Corporation) at an output of 100 W for 30 seconds. A 100 nm thick layer of Al was vapor-deposited onto the contact resistance evaluation substrate to form a second electrode (reference numeral 6). (Fig. 1(3)) Finally, a cap-shaped glass plate was attached using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to seal the substrate, which was then used for evaluation as a contact resistance evaluation substrate. The evaluation substrate had four effective substrate areas (reference numeral 5) within a single substrate, and each effective substrate area (reference numeral 5) had a cured resin (reference numeral 4) with 55 rectangular openings measuring 260 μm in length and 70 μm in width, and a first electrode (reference numeral 2) and a second electrode (reference numeral 6) were connected through these openings.

[0108] The terminals of a resistance tester (Keithley SourceMeter 2400) were connected to the first electrode (reference numeral 2) and the auxiliary electrode (reference numeral 3) for extracting the second electrode of the contact resistance evaluation board fabricated by the above method, and the contact resistance of the openings was measured for four locations on the substrate's effective area (reference numeral 5), and the average value was calculated. The results were judged as follows, and A, B, and C, which indicated a contact resistance of 60 Ω or less, were judged to be pass. A: Contact resistance 54 Ω or less B: Contact resistance greater than 54 Ω and less than 57 Ω C: Contact resistance greater than 57 Ω and less than 60 Ω D: Contact resistance greater than 60 Ω and less than 63 Ω E: Contact resistance greater than 63 Ω or not measurable.

[0109] (7) Sensitivity The resin composition was applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), and baked at 120°C for 2 minutes to produce a pre-baked film with a film thickness of 3.0 μm. Thereafter, using an i-line stepper exposure apparatus (NSR-2005i9C manufactured by Nikon Corporation), the wafer was exposed to light at an exposure dose of 50 to 300 mJ / cm through a mask having a pattern of 10 μm contact holes. ２ in the range of 5 mJ / cm ２ After the exposure, the film was developed using the ACT-8 developing device with a 2.38% by mass aqueous solution of TMAH as a developer until the film thickness was reduced to 0.5 μm, and then rinsed with pure water and spun off to dry, thereby obtaining a pattern.

[0110] The obtained pattern was observed at a magnification of 20 times using a microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined. The smaller the minimum exposure dose, the higher the sensitivity. ２ The following items are considered to have extremely good sensitivity (3 points), 120 mJ / cm ２ exceeding 160 mJ / cm ２ The following are considered to have good sensitivity (2 points): 160 mJ / cm ２ Anything above this was rated as poor sensitivity (1 point).

[0111] (8) Frozen Storage Stability 10 g of the resin composition of each Example and Comparative Example was placed in a 32 mL polypropylene vial and stored in a freezer at -16°C for 14 days. The vial was then removed from the freezer and thawed at room temperature of 23°C for 1 hour. The resin composition was visually inspected for abnormalities such as the occurrence of precipitates or gelation in this state (hereinafter also referred to as "post-frozen"). The sensitivity of the resin composition after freezing that had no abnormalities was evaluated and compared with the sensitivity evaluation results of the resin composition in an unfrozen state (hereinafter also referred to as "before freezing"). A minimum exposure change of ±5% or less was evaluated as having very good frozen storage stability (4 points); a minimum exposure change of more than ±5% but not more than ±10% was evaluated as having good frozen storage stability (3 points); a minimum exposure change of more than ±10% was evaluated as having poor frozen storage stability (2 points); and a minimum exposure change of more than ±10% was evaluated as having very poor frozen storage stability (1 point) after freezing. A score of 3 or more was evaluated as passing.

[0112] (9) Folding Endurance First, a 25 μm Kapton® film cut to 10 cm × 10 cm was fixed with Kapton® tape so as to cover one side of a 10 cm × 10 cm, 0.5 mm thick glass substrate. The resin composition was applied to the Kapton® film on the glass substrate by spin coating using a spinner (manufactured by Mikasa Co., Ltd.) and baked at 120°C for 2 minutes to produce a pre-baked film with a thickness of 5 μm. The film was then developed using a 2.38% by mass aqueous TMAH solution as a developer under conditions such that the film loss was 0.5 μm, followed by rinsing with pure water. The developed substrate was then heat-cured for 1 hour at a predetermined temperature under a nitrogen stream (oxygen concentration of 20 ppm by volume or less) using a clean oven CLH-21CD-S. After heat curing, the approximately 4 μm thick "Kapton" (registered trademark) film with the cured film was removed from the glass substrate, and this two-layer film was shredded into 1 cm x 2 cm pieces. The shredded laminated film was folded in half, with the "Kapton" (registered trademark) film side facing inward and the cured film side facing outward, and the long side was divided in half. The film was then placed in a jig with a groove of a predetermined depth, covered with a lid, left to stand for 1 minute, and then removed. The depth of the groove was equivalent to twice the bending radius. The groove depth was evaluated under two conditions: 0.4 mm and 0.2 mm. The laminated film removed from the jig was observed with a microscope MX61 (manufactured by Olympus Corporation) to determine whether or not there was a crack at the folding position. Three laminate films were evaluated under each condition, and those with no cracks on all three were judged as extremely good (3 points), those with cracks observed on one film were judged as good (2 points), and those with cracks observed on two or three films were judged as poor (1 point). Furthermore, the overall judgment of folding endurance was as follows: those with extremely good groove depths of both 0.4 mm and 0.2 mm were judged as having very good folding endurance (4 points), those with extremely good groove depths of 0.4 mm and good groove depths of 0.2 mm were judged as having good folding endurance (3 points), those with good groove depths of both 0.4 mm and 0.2 mm were judged as having normal folding endurance (2 points), and those with poor groove depths of either 0.4 mm or 0.2 mm or both were judged as having poor folding endurance (1 point).

[0113] (10) Fluorine content of the cured product The resin composition of each example and comparative example was applied to a 6-inch silicon wafer by spin coating using a spinner (1H-DX, manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 2 minutes to produce a resin film with a thickness of 5 μm. This wafer with the resin film was heat-cured for 1 hour at a predetermined temperature under a nitrogen gas flow (oxygen concentration 20 ppm or less) using a clean oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.). The film after heat curing was scraped to collect the cured product powder, and the fluorine content (mass%) of the cured product was determined using a total fluorine quantification method using combustion ion chromatography (ASTM D7359).

[0114] [Synthesis Examples] The compounds containing a 1,1'-spirobiindane structure used in the synthesis examples are shown below. Among them, SBI-1, SBI-2, and SBI-3 are diamines corresponding to the diamine residue represented by formula (1). SBI-1: 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane SBI-2: 6,6'-diamino-3,3,3',3'-tetramethyl-1,1'-spirobiindane SBI-3: 6,6'-bis(4-amino-3-hydroxyphenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane SBI-4: 5,5'-diamino-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane SBI-5: 6,6'-dicarboxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane SBI-5Bt: A dicarboxylic acid derivative obtained by reacting 6,6'-dicarboxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane with 1-hydroxy-1,2,3-benzotriazole in a molar ratio of 1:2.

[0115]

[0116] Synthesis Example 1 Synthesis of Polyamic Acid Ester Resin (A-1) Under a dry nitrogen stream, 0.5 g (0.001 mol) of SBI-1, 19.1 g (0.074 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter, BAP), and 1.2 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, SiDA) were dissolved in 300 g of N-methyl-2-pyrrolidone (hereinafter, NMP). 31.0 g (0.1 mol) of bis(3,4-dicarboxyphenyl)ether dianhydride (hereinafter, ODPA) was added to the solution along with 20 g of NMP, and the mixture was allowed to react at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 4.4 g (0.04 mol) of 4-aminophenol (hereinafter, AP) was added as an end-capping agent along with 10 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, 21.4 g (0.18 mol) of N,N-dimethylformamide dimethyl acetal was added, and the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was cooled to room temperature and then poured into 5 L of water to obtain a precipitate. This precipitate was collected by filtration, and a washing operation of adding 5 L of water and collecting the precipitate by filtration was repeated three times, followed by drying in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyamic acid ester resin (A-1).

[0117] Synthesis Example 2 Synthesis of Polyimide Resin (A-4) Under a dry nitrogen stream, 17.2 g (0.035 mol) of SBI-1, 12.9 g (0.05 mol) of BAP, 1.2 g (0.005 mol) of SiDA, and 2.2 g (0.02 mol) of AP as an end-capping agent were dissolved in 300 g of NMP. 31.0 g (0.1 mol) of ODPA was added to the mixture along with 20 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 4 hours. Thereafter, 10 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was cooled to room temperature and then poured into 5 L of water to obtain a precipitate. This precipitate was collected by filtration, and after three washing operations in which 5 L of water was added and the precipitate was collected by filtration, the mixture was dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide resin (A-4).

[0118] Synthesis Example 3: Synthesis of Polyamic Acid Resin (A-7) Under a dry nitrogen stream, 17.2 g (0.035 mol) of SBI-1, 12.9 g (0.05 mol) of BAP, and 1.2 g (0.005 mol) of SiDA were dissolved in 300 g of NMP. 31.0 g (0.1 mol) of ODPA was added to the solution along with 20 g of NMP, and the mixture was allowed to react at 20°C for 1 hour, followed by a reaction at 70°C for 2 hours. After the temperature was lowered to 50°C, 2.2 g (0.02 mol) of 4-aminophenol (hereinafter referred to as AP) was added as an end-capping agent along with 10 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. After the reaction was completed, the solution was cooled to room temperature and then poured into 5 L of water to obtain a precipitate. This precipitate was collected by filtration, and a washing operation of adding 5 L of water and filtering the precipitate was repeated three times. The precipitate was then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyamic acid resin (A-7).

[0119] Synthesis Example 4 Synthesis of Polybenzoxazole Precursor Resin (A-17) Under a dry nitrogen stream, 17.2 g (0.035 mol) of SBI-1, 12.9 g (0.05 mol) of BAP, 1.2 g (0.005 mol) of SiDA, and 2.2 g (0.02 mol) of AP as an end-capping agent were dissolved in 250 g of NMP. While stirring this solution in an ice bath, 29.5 g (0.1 mol) of 4,4'-diphenyl ether dicarboxylic acid dichloride (hereinafter also referred to as OBC) dissolved in 60 g of NMP was added dropwise over 30 minutes. After stirring for an additional hour, the ice bath was replaced with a water bath and the mixture was stirred at 50°C for 2 hours. After stirring was completed, the solution was cooled to room temperature and then poured into 5 L of water to obtain a precipitate. This precipitate was collected by filtration, and a washing procedure of adding 5 L of water and then filtering to collect the precipitate was repeated three times. The precipitate was then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polybenzoxazole precursor resin (A-17).

[0120] Synthesis Example 5 Synthesis of Polybenzoxazole Precursor Resin (A'-22) Under a dry nitrogen stream, 47.9 g (0.08 mol) of a dicarboxylic acid derivative (SBI-5Bt) obtained by reacting SBI-5 and 1-hydroxy-1,2,3-benzotriazole in a molar ratio of 1:2, 17.3 g (0.08 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl (hereinafter referred to as DABP), and 7.3 g (0.02 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as 6FAP) were dissolved in 250 g of NMP and stirred for 12 hours at 55°C. Next, 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride (hereinafter referred to as NA) as an end-capping agent was added together with 10 g of NMP, and the mixture was further stirred at 55°C for 12 hours. After stirring was completed, the solution was cooled to room temperature, and then the reaction mixture was filtered. The filtrate was poured into 5 L of a mixed solution of water / methanol = 3 / 1 (volume ratio) to obtain a precipitate. This precipitate was collected by filtration, and a washing procedure of adding 5 L of water and filtering the collected precipitate was repeated three times, and then the precipitate was dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polybenzoxazole precursor resin (A'-22).

[0121] Synthesis Example 6 Synthesis of Polybenzoxazole Precursor Resin (A'-24) Under a dry nitrogen stream, 33.8 g (0.1 mol) of SBI-4 and 9.33 g (0.22 mol) of lithium chloride were dissolved in 250 g of NMP. While stirring in an ice bath, 20.3 g (0.1 mol) of isophthaloyl chloride (hereinafter, IPC) was added to this solution, and the mixture was stirred in an ice bath for 1 hour and at 23°C for 24 hours. After stirring was completed, the solution was poured into 5 L of water to obtain a precipitate. This precipitate was collected by filtration, and a washing operation of adding 5 L of water and filtering the precipitate was repeated three times. After that, the mixture was dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polybenzoxazole precursor resin (A'-24).

[0122] Synthesis Examples 7 to 22 Synthesis of Polyamic Acid Ester Resins (A-2 to A-3, A-5 to A-6, A-8 to A-13, A-15 to A-16, A'-18 to A'-21) Powders of polyamic acid ester resins (A-2, A-3, A-5, A-6, A-8, A-9, A-10, A-11, A-12, A-13, A-15, A-16, A'-18, A'-19, A'-20, and A'-21) were obtained in the same manner as in Synthesis Example 1, except that the diamines, acid dianhydrides, end-capping agents, and N,N-dimethylformamide dimethyl acetal used were replaced as shown in Table 1.

[0123] Synthesis Example 23 Synthesis of Polyimide Resin (A-14) Powder of polyimide resin (A-14) was obtained in the same manner as in Synthesis Example 2, except that the diamine, acid dianhydride, and end-capping agent used were replaced as shown in Table 1.

[0124] Synthesis Example 24 Synthesis of polybenzoxazole precursor resin (A'-23) Powder of polybenzoxazole precursor resin (A'-23) was obtained in the same manner as in Synthesis Example 4, except that the diamine, dicarboxylic acid derivative, and end-capping agent used were replaced as shown in Table 1.

[0125]

[0126]

[0127] The abbreviations for compounds not described in the above synthesis examples are as follows: BA3B: 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane DABS: bis(3-amino-4-hydroxyphenyl)sulfone PMDA: pyromellitic dianhydride TDA-100: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride BSAA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride PMDA-H: 1,2,4,5-cyclohexanetetracarboxylic dianhydride For the components (a) (A-1 to A-17) and other resins (A'-18 to A'-24) obtained in the above Synthesis Examples, Table 2 shows the type, the amount (mol %) of diamine residues represented by formula (1) relative to 100 mol % of all diamine residues, the amount (mol %) of diamine residues represented by formula (4), the presence or absence of tetracarboxylic acid residues represented by formula (2), and the presence or absence of dicarboxylic acid residues represented by formula (3).

[0128]

[0129] The components (a) (A-1 to A-17) and other resins (A'-18 to A'-24) obtained in the above synthesis examples were evaluated for the content of (II) amic acid ester structure in the resin and the content of (III) imide structure in the resin, and the results are shown in Table 3. In Table 3, "-" indicates that the item was not evaluated.

[0130]

[0131] Synthesis Example 25: Synthesis of quinone diazide compound (B-1) Under a dry nitrogen stream, 42.4 g (0.1 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 72.3 g (0.27 mol) of 5-naphthoquinone diazide sulfonic acid chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. To this solution, 25.0 g of triethylamine mixed with 100 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration and washed with 1 L of 1% aqueous hydrochloric acid. The mixture was then washed twice with 2 L of water. This precipitate was dried in a vacuum dryer to obtain a quinone diazide compound (B-1) represented by the following formula.

[0132]

[0133] [Other Components Used in Examples and Comparative Examples] As the photopolymerization initiator (b2) of the photosensitizer (b), ADEKA ARCLES (registered trademark) NCI-831 (trade name, manufactured by ADEKA CORPORATION, oxime ester photopolymerization initiator) (B-2) was used in the examples.

[0134] (d) As a compound having a polymerizable unsaturated bond group, dipentaerythritol hexaacrylate (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.) (D-1) was used in the examples.

[0135]

[0136] As the component (e), HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) (E-1) and "Showfree" (registered trademark) BATG (trade name, manufactured by Showa Denko K.K.) (E-2)) were used in the examples.

[0137]

[0138] As the component (f), 3-methoxy-N,N-dimethylpropionamide (F-1) was used in the examples.

[0139]

[0140] [Preparation of Resin Compositions] Each component according to the composition shown in Tables 4 to 7 was placed in a 32 mL polypropylene vial, and mixed using a stirring and degassing apparatus (ARE-310, manufactured by Thinky Corporation) under conditions of 10 minutes of stirring and 1 minute of degassing. After dissolution, the mixture was filtered through a 0.2 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) to prepare resin compositions (W-1 to 53). In Tables 4 to 7, "GBL" represents γ-butyrolactone, "PGME" represents propylene glycol monomethyl ether, and "-" represents that the compound was not added. In Table 6, F-1 of the (f) component was added as a solution in γ-butyrolactone. The ratio of (F-1) / GBL shown in Table 6 refers to the mass ratio of F-1 and GBL in the solution.

[0141]

[0142]

[0143]

[0144]

[0145] [Examples 1 to 24, Comparative Examples 1 to 7] The prepared resin compositions were used to evaluate thinner solubility, contact resistance, and sensitivity using the methods described above, and the results are shown in Tables 8 and 9. The heat curing temperatures used to prepare the contact resistance evaluation boards are also shown in the tables.

[0146]

[0147]

[0148] All of the samples shown in Examples 1 to 24 had good results of 3 points for thinner solubility, good results of contact resistance of 60 Ω or less, and good results of sensitivity of 2 points or more.

[0149] On the other hand, the results of Comparative Examples 1 to 7 were poor in at least one of thinner solubility and contact resistance. Of these, the fluorine content of the cured products of Examples 5, 21 to 24 and Comparative Example 1 was evaluated, and the results are shown in Table 10. The heat curing temperature of the samples used to evaluate the fluorine content of the cured products was 260°C, the same as in the contact resistance evaluation.

[0150]

[0151] As shown in Table 10, Examples 5, 21, and 22, in which the fluorine content of the cured product was 0% by mass or more and 0.5% by mass or less, showed good results for contact resistance, graded B, and Example 5, in which the fluorine content of the cured product was 0% by mass, showed the best result.

[0152] Examples 25 to 34 Using the prepared resin compositions, the content of component (f) and frozen storage stability were evaluated by the above-mentioned method. The results are shown in Table 11.

[0153]

[0154] All of the samples shown in Examples 25 to 34 had good results in terms of frozen storage stability, with a score of 3 or higher. Among these, Examples 26 to 28 and 31 to 33, in which the content of component (f) was 0.01 parts by mass or more and 5 parts by mass or less, had extremely good results in terms of contact resistance, with a score of 4 in terms of frozen storage stability.

[0155] Examples 35 to 46 The resin compositions thus prepared were used to evaluate the folding endurance and sensitivity according to the methods described above. The results are shown in Table 12.

[0156]

[0157] The folding endurance of Examples 37 to 40 and Examples 43 to 46 all achieved a good overall rating of 3 or more points. On the other hand, Examples 35, 36, 41, and 42, which contained less than 10 parts by mass of component (e) per 100 parts by mass of component (a), achieved a fair or poor overall rating of 2 or less points. Furthermore, Examples 40 and 46, which contained more than 50 parts by mass of component (e) per 100 parts by mass of component (a), achieved very good folding endurance but poor sensitivity.

[0158] The resin composition of the present invention is suitably used for bank layers of organic EL display devices, planarizing layers of TFT substrates for driving organic EL display devices, surface protection layers and interlayer insulating layers of semiconductor elements, wiring protection and insulating layers of circuit boards, on-chip microlenses of solid-state imaging devices, and planarizing layers for various displays and solid-state imaging devices.

[0159] The cured product of the present invention is capable of suppressing the contact resistance of electrodes after ashing to a low level, and is therefore suitable for use as a bank layer in an organic EL display device, a planarizing layer in a TFT substrate for driving an organic EL display device, a surface protection layer or interlayer insulating layer in a semiconductor element, a wiring protection insulating layer in a circuit board, an on-chip microlens in a solid-state imaging device, and a planarizing layer for various displays and solid-state imaging devices.

[0160] The display device or semiconductor device of the present invention comprises the cured product of the present invention, which can reduce the contact resistance of the electrodes after ashing, and is therefore suitable for use as a display device or semiconductor device that reduces the contact resistance of the electrodes and provides stable driving characteristics.

[0161] 1: Substrate 2: First electrode 3: Auxiliary electrode 4: Resin cured product 5: Substrate effective area 6: Second electrode

Claims

1. A resin composition comprising the following components (a) to (c), in which component (a) contains 1 mol % or more and 80 mol % or less of diamine residues represented by formula (1) relative to 100 mol % of all diamine residues contained in the resin skeleton of component (a): Component (a): at least one resin selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof; Component (b): photosensitizer; Component (c): solvent. (In formula (1), R １ ~R ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom; ２ -, -C(CH ３ ) ２ -, -O-, -S-, -SO ２ p, q, r and s each independently represent an integer of 0 or 1. * represents a bond.

2. The resin composition according to claim 1, wherein the resin skeleton of the component (a) further contains one or more residues selected from the group consisting of tetracarboxylic acid residues represented by formula (2) and dicarboxylic acid residues represented by formula (3). (In formula (2) and formula (3), * represents a bond.) 3. The resin composition according to claim 1 or 2, wherein the skeleton of the resin of component (a) further contains a diamine residue represented by formula (4), and the skeleton of the resin of component (a) contains 1 to 50 mol % of diamine residues represented by formula (1) and 50 to 95 mol % of diamine residues represented by formula (4) relative to 100 mol % of all diamine residues in the skeleton of the resin of component (a). (In formula (4), Y is a divalent organic group having 1 to 20 carbon atoms, -O-, -S-, -SO ２ - or a single bond; R １１ and R １２ Each independently represents -CH ２ -, -C(CH ３ ) ２ represents -, -O-, -NHC(=O)-, or -C(=O)NH-. Each t independently represents an integer of 0 or 1. However, formula (4) does not include the structure represented by formula (1). * represents a bond.) 4. The resin composition according to claim 1 or 2, wherein the component (a) is a polyimide precursor or a polyimide, and when the content of (I) amic acid structure is defined as u mol %, the content of (II) amic acid ester structure is defined as v mol %, and the content of (III) imide structure is defined as w mol %, relative to 100 mol % in total of (I) amic acid structure, (II) amic acid ester structure, and (III) imide structure in the resin skeleton of the component (a), the following conditions are satisfied: 0≦v≦80, and 10≦w≦80 (with the proviso that u+v+w=100).

5. The resin composition according to claim 1 or 2, wherein the photosensitizer of the component (b) contains a quinone diazide compound (b1).

6. The resin composition according to claim 1 or 2, wherein the photosensitizer of component (b) contains (b2) a photopolymerization initiator, and further contains (d) a compound having a polymerizable unsaturated bond group.

7. The resin composition according to claim 1 or 2, further comprising the following component (e): 10 to 50 parts by mass of component (e) per 100 parts by mass of component (a): Component (e): a compound having one or more groups selected from the group consisting of a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, and an isocyanate group.

8. The resin composition according to claim 1 or 2, wherein the component (a) does not contain elemental fluorine and further contains the following component (f), wherein the component (f) is contained in an amount of 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the component (a). Component (f): A compound represented by formula (5): (In formula (5), R １３ ~R １５ each independently represents an alkyl group having 1 to 4 carbon atoms; R １６ represents an alkylene group having 1 to 4 carbon atoms.

9. A cured product obtained by curing the resin composition according to claim 1 or 2.

10. The cured product according to claim 9, having a fluorine content of 0% by mass or more and 0.5% by mass or less.

11. A display device comprising the cured product according to claim 9.

12. A semiconductor device comprising the cured product according to claim 9.