Resin composition, cured product, organic el display device, and semiconductor device

Abstract

The present invention addresses the problem of providing a resin composition that can be patterned with high sensitivity, without causing residue or peeling, using a conventional 2.38 mass% aqueous solution of TMAH as a developing solution.　Provided is a resin composition which contains: a polyimide resin (A) having a specific structure and an amic acid structure; and a photosensitive compound (B). The proportion of the amic acid structure in the polyimide resin (A) is 5-50%.

Description

Resin composition, cured product, organic EL display device, and semiconductor device

[0001] The present invention relates to a resin composition, a cured product using the same, and an organic EL display device and a semiconductor device that include the cured product.

[0002] Heat-resistant resins such as polyimide and polybenzoxazole have excellent mechanical properties, heat resistance, chemical resistance, and electrical insulation properties, and are therefore used in surface protection films and interlayer insulating films of semiconductor devices such as large-scale integrated circuits (LSIs), and planarizing layers and bank layers of organic electroluminescence (hereinafter referred to as organic EL) display devices.

[0003] Resin compositions used for these applications are required to impart high reliability to organic EL display devices and semiconductor devices, as well as to have high photosensitivity in order to shorten exposure time for reasons such as increasing the size of substrates and improving productivity.

[0004] In response to such a demand for photosensitivity, resin compositions that can achieve high sensitivity have been investigated, including mixing a novolac resin or a polyhydroxystyrene resin with a polyimide resin or a polybenzoxazole resin (e.g., Patent Documents 1 and 2), and using a specific acid dianhydride with high transparency as a raw material for a polyimide resin (e.g., Patent Document 3).

[0005] JP 2005-352004 A JP 2014-59463 A JP 2008-297231 A

[0006] However, when the materials proposed in the above-mentioned patent documents are developed with a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which is a general-purpose alkaline developer, residues are generated in pattern openings and peeling easily occurs between the material and the underlying substrate, particularly SiN, and it is difficult to say that the materials have sufficient performance from the viewpoint of production stability. In particular, the material proposed in Patent Document 3 does not provide a good pattern when developed with a 2.38 mass % aqueous solution of TMAH, and it was necessary to use a non-general-purpose developer, such as one containing an organic solvent such as an alcohol or a glycol.

[0007] In order to solve the above problems, the present invention has the following configuration: [1] A resin composition containing a polyimide resin (A) having a structure represented by either formula (1) or formula (2) and an amic acid structure, and a photosensitive compound (B), in which the ratio of the amic acid structure in the polyimide resin (A) is 5% or more and 50% or less.

[0008]

[0009] (In formula (1) and formula (2), X １ and X ２ each independently represents a tetravalent organic group containing at least one aromatic ring having 6 to 40 carbon atoms; R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding site. [2] X in the formula (1) and formula (2) １ and X ２ At least one of the above is a structure represented by formula (3).

[0010]

[0011] (In formula (3), R ３ is a direct bond, -SO ２ -, -O-, -S-, -CO-, -C(CF ３ ) ２ - or a hydrocarbon group having 1 to 20 carbon atoms, R ４ and R ５ each independently represents a chlorine atom, a fluorine atom, a cyano group, a nitro group, or a trifluoromethyl group, and a and b each independently represent an integer of 0 to 3. １ indicates the bond to the nitrogen atom, * ２ represents a bond to an oxygen atom.) [3] R in the formula (3) ３ The resin composition according to [2] above, wherein is a structure represented by formula (9) or formula (10):

[0012]

[0013] (In formulas (9) and (10), R １９represents an alkyl group having 1 to 4 carbon atoms, c represents an integer of 1 to 3, d represents 1 or 2, R ２０ and R ２１ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents the point of attachment to the aromatic ring. ２０ and R ２１ are not the same structure.) [4] The resin composition according to any one of [1] to [3] above, wherein the polyimide resin (A) has an amic acid ester structure, and the ratio of the amic acid ester structure in the polyimide resin (A) is 20% or more and 90% or less. [5] The resin composition according to any one of [1] to [4] above, further containing a thermal crosslinking agent (C). [6] The resin composition according to [5] above, wherein the thermal crosslinking agent (C) contains one or more thermal crosslinking agents selected from the group consisting of an isocyanuric ring structure-containing epoxy thermal crosslinking agent, an alicyclic epoxy thermal crosslinking agent, and an aliphatic epoxy thermal crosslinking agent. [7] The resin composition according to any one of [1] to [6] above, further containing a solvent (D), wherein the solvent (D) is a solvent (D1) represented by formula (11) and / or a solvent represented by formula (12).

[0014]

[0015] (In formulas (11) and (12), a plurality of R ２２ each independently represents an alkyl group having 1 to 6 carbon atoms; R ２３represents an alkyl group having 2 to 6 carbon atoms.) [8] The resin composition according to any one of [1] to [7] above, further comprising a solvent (D), wherein the solvent (D) includes a solvent (D2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or higher and 200°C or lower. [9] The resin composition according to [7] above, wherein the solvent (D) includes a solvent (D2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or higher and 200°C or lower, and wherein the content ratio Y / X, where X (parts by mass) is the content of the solvent (D1) in the resin composition and Y (parts by mass) is 1 or higher and 1,000 or lower.

[10] A cured product obtained by curing the resin composition according to any one of [1] to [9] above.

[11] An organic EL display device comprising the cured product according to

[10] above.

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

[10] above.

[0016] The resin composition of the present invention can be used in a commonly used 2.38 mass % TMAH aqueous solution as a developer, and can provide a resin composition that can be patterned with high sensitivity without causing residue or peeling, and is suitable for use in planarizing layers and bank layers of organic EL display devices, surface protective films of semiconductor devices, and interlayer insulating films.

[0017] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to examples.

[0018] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0019] The resin composition of the present invention is a resin composition containing a polyimide resin (A) having a structure represented by either formula (1) or formula (2) and an amic acid structure, and a photosensitive compound (B), wherein the ratio of the amic acid structure in the polyimide resin (A) is 5% or more and 50% or less.

[0020]

[0021] (In formula (1) and formula (2), X １ and X ２ each independently represents a tetravalent organic group containing at least one aromatic ring having 6 to 40 carbon atoms; R １ and R２ Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding site.) Each component will be described in detail below, but the present invention is not limited thereto.

[0022] <Polyimide Resin (A)> The polyimide resin (A) is a polyimide resin having a structure represented by either formula (1) or formula (2) and an amic acid structure, and the ratio of the amic acid structure in the polyimide resin (A) is 5% or more and 50% or less. The ratio of the amic acid structure in the polyimide resin (A) referred to here is a molar ratio, as will be described in detail later.

[0023]

[0024] (In formula (1) and formula (2), X １ and X ２ each independently represents a tetravalent organic group containing at least one aromatic ring having 6 to 40 carbon atoms; R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding site.) In the present invention, the definition of polyimide resin includes not only imide structures formed by closure with imide rings, but also structures before closure with imide rings, i.e., amic acid structures or amic acid ester structures.

[0025] Examples of the amic acid structure include a structure obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and specifically refers to a structure represented by the following formula (4):

[0026]

[0027] (In formula (4), A １ represents a trivalent organic group having 4 to 50 carbon atoms, and B １ represents a divalent organic group having 2 to 50 carbon atoms, and A １ and B １does not include any of an amic acid structure, an amic acid ester structure, and an imide structure.) Examples of the amic acid ester structure include structures obtained by adding an esterifying agent to the above amic acid structure to esterify all or part of the carboxylic acid moieties of the amic acid structure, and specifically refer to a structure represented by the following formula (5):

[0028]

[0029] (In formula (5), A ２ represents a trivalent organic group having 4 to 50 carbon atoms, and B ２ represents a divalent organic group having 2 to 50 carbon atoms, and R ６ represents a monovalent organic group having 1 to 20 carbon atoms, and A ２ and B ２ does not include an amic acid structure, an amic acid ester structure, or an imide structure.) Examples of esterifying agents include a method using a catalyst such as triethylamine or dimethylaminopyridine with a compound having an alcohol group such as 2-hydroxyethyl methacrylate, methanol, or ethanol, and a method using a catalyst-free compound such as N,N-dialkylformamide dimethyl acetal, which contains tetracarboxylic acid and / or its derivative residues and diamine and / or its derivative residues. The ester structure is preferably an alkyl ester structure, and the alkyl group preferably has a molecular weight of 100 or less. Using a low-molecular-weight, easily volatile alkyl group reduces the shrinkage rate during thermal curing, resulting in excellent planarization properties when a resin coating is formed on an uneven surface. Specifically, the ester structure is preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

[0030] Examples of the imide structure include structures in which the above-mentioned amic acid structure or amic acid ester structure is ring-closed into an imide ring by dehydration ring-closure through heating or a reaction using an acid or a base, and specifically refer to a structure represented by the following formula (6):

[0031]

[0032] (In formula (6), A ３ represents a trivalent organic group having 4 to 50 carbon atoms, and B３ represents a divalent organic group having 2 to 50 carbon atoms, and A ３ and B ３ does not include any of an amic acid structure, an amic acid ester structure, and an imide structure.) The polyimide resin (A) may be copolymerized with a structure other than an amic acid structure, an amic acid ester structure, and an imide structure, and specific examples thereof include amide, benzoxazole, benzimidazole, benzothiazole, and precursor structures thereof.

[0033] To obtain a polyimide resin containing a structure represented by either formula (1) or formula (2), an alicyclic tetracarboxylic dianhydride represented by formula (7) is used as the acid dianhydride raw material.

[0034]

[0035] (In formula (7), X ３ represents a tetravalent organic group containing at least one aromatic ring having 6 to 40 carbon atoms.) The polyimide resin containing the structure represented by either formula (1) or formula (2) can be obtained by １ and X ２ At least one of the above is preferably a structure represented by formula (3).

[0036]

[0037] (In formula (3), R ３ is a direct bond, -SO ２ -, -O-, -S-, -CO-, -C(CF ３ ) ２ - or a hydrocarbon group having 1 to 20 carbon atoms, R ４ and R ５ each independently represents a chlorine atom, a fluorine atom, a cyano group, a nitro group, or a trifluoromethyl group, and a and b each independently represent an integer of 0 to 3. １ indicates the bond to the nitrogen atom, * ２ represents a bond with an oxygen atom. ３ is preferably a structure represented by formula (9) or formula (10).

[0038]

[0039] In formulas (9) and (10), R １９ represents an alkyl group having 1 to 4 carbon atoms, c represents an integer of 1 to 3, d represents 1 or 2, R ２０ and R ２１ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents the point of attachment to the aromatic ring. ２０ and R ２１ are not the same structure. When c is 2 or 3, R １９ may be different alkyl groups having 1 to 4 carbon atoms.

[0040] R in the formula (3) ３ By having a structure represented by formula (9) or formula (10), peeling does not occur after development, and the storage stability of the resin composition can be improved.

[0041] Among them, in the formula (9), the R １９ The total number of carbon atoms in the formula (10) is 1 or more and 5 or less, and ２０ and the number of carbon atoms in R ２１ In the formula (9), the total number of carbon atoms in the R １９ The total number of carbon atoms in the formula (9) is 1 or more and 5 or less. １９ If there are multiple R １９ The total number of carbon atoms in the R ２０ and the number of carbon atoms in R ２１ The total number of carbon atoms in R is 3 or more and 10 or less. ２０ and R ２１ The total number of carbon atoms in each of the R groups is 3 or more and 10 or less. １９ , R ２０ , R ２１ When the number of carbon atoms is within the above range, a photosensitive resin composition having good metal adhesion and solvent solubility after pressure cooker test (PCT) treatment can be obtained without causing development residue or deterioration in sensitivity, which is preferable.

[0042] R is a structure represented by formula (9) or formula (10) ３ Specific examples of the structure include, but are not limited to, the structures shown below.

[0043]

[0044] (* represents a bonding point on the aromatic ring.) As the alicyclic tetracarboxylic acid dianhydride represented by formula (7), it is preferable to use an alicyclic tetracarboxylic acid dianhydride represented by formula (8).

[0045]

[0046] (In formula (8), R ７ is a direct bond, -SO ２ -, -O-, -S-, -CO-, -C(CF ３ ) ２ - or a hydrocarbon group having 1 to 20 carbon atoms, R ８ and R ９ each independently represents a chlorine atom, a fluorine atom, a cyano group, a nitro group, or a trifluoromethyl group, and c and d each independently represent an integer of 0 to 3. ７ is preferably a structure represented by formula (9) or formula (10).

[0047] In the structure represented by formula (8), the phenolic hydroxyl group, which is an acidic group, is -R ７ One phenolic hydroxyl group is located on each of two aromatic rings separated by an atom -. The phenolic hydroxyl groups have an appropriate interatomic distance, which is advantageous in that good alkaline developability is obtained and processing can be performed with high sensitivity without causing residue or peeling.

[0048] Among the structures represented by formula (8), a structure containing no fluorine atom is preferred in that it does not peel off after development.

[0049] Specific examples of the alicyclic tetracarboxylic dianhydrides represented by formula (8) that do not contain a fluorine atom include, but are not limited to, the structures shown below.

[0050]

[0051]

[0052]

[0053] Specific examples of the alicyclic tetracarboxylic dianhydrides represented by formula (8) containing a fluorine atom include, but are not limited to, the structures shown below.

[0054]

[0055] Among the alicyclic tetracarboxylic dianhydrides represented by formula (8) having a structure containing no fluorine atom, the following structure is particularly preferred in terms of particularly good sensitivity, good storage stability of the resin composition, and no peeling after development.

[0056]

[0057] Specific examples of the alicyclic tetracarboxylic dianhydride represented by formula (7) other than the one represented by formula (8) include, but are not limited to, the structures shown below.

[0058]

[0059] The alicyclic tetracarboxylic dianhydride represented by formula (7) is not particularly limited, and commercially available products or those obtained by conventionally known production methods (see, for example, JP-A-2008-297231) can be used.

[0060] In the resin composition of the present invention, the polyimide resin (A) has an amic acid structure, and the ratio of the amic acid structure in the polyimide resin (A) is 5% or more and 50% or less. The ratio of the amic acid structure in the polyimide resin (A) means the molar ratio of the amic acid structure to the sum of all the amic acid structures, amic acid ester structures, and imide structures in the polyimide resin (A).

[0061] When the ratio of the amic acid structure is 5% or more and 50% or less, pattern processing can be performed with high sensitivity without causing residue or peeling when using a commonly used 2.38% by mass TMAH aqueous solution as a developer. This is because the presence of an appropriate amount of amic acid structure results in good pattern processability without causing either residue due to insufficient alkaline developability or peeling due to excessive alkaline developability or insufficient adhesion to the underlying substrate such as SiN. The ratio of the amic acid structure is preferably 10% or more, more preferably 15% or more, in terms of not causing residue. Furthermore, it is preferably 40% or less, more preferably 30% or less, in terms of not causing peeling. A method for calculating the ratio of the amic acid structure will be described later.

[0062] In the resin composition of the present invention, the polyimide resin (A) preferably has an amic acid ester structure, and the ratio of the amic acid ester structure in the polyimide resin (A) is preferably 20% or more and 90% or less. The ratio of the amic acid ester structure is preferably 20% or more, more preferably 35% or more, and even more preferably 50% or more, in order to prevent peeling. Furthermore, the ratio is preferably 90% or less, more preferably 80% or less, and even more preferably 75% or less, in order to prevent residues from being generated. The method for calculating the ratio of the amic acid ester structure will be described later.

[0063] The ratio of the amic acid ester structure in the polyimide resin (A) (hereinafter referred to as the esterification ratio) can be determined by the following method: First, the resin is dissolved in a heavy solvent such as deuterated dimethyl sulfoxide, １By measuring with a H-NMR (nuclear magnetic resonance spectrometer), the esterification rate (%) can be calculated from the area ratio of the integrated value of the peak derived from the aromatic protons of the resin to the peak derived from the methyl protons of the carboxylic acid alkyl ester. For example, in the case of a resin obtained by reacting 4,4'-oxydianiline with 4,4'-oxydiphthalic dianhydride and then methyl-esterifying a portion of the amide acid structure with dimethylformamide dimethyl acetal (see JP 2019-20709 A, paragraphs 0137 and 0139), when the integrated value of the aromatic protons in the repeating structure of the polyimide resin is 14 as the reference, the integrated value of the methyl protons of the methyl ester located near 3.8 ppm will be 6 if the esterification rate is 100%. The esterification rate can be calculated from the ratio of this to the actually measured integrated value A of the methyl protons. Esterification rate (%) = 100 × A / 6.

[0064] The ratio of the imide structure in the polyimide resin (A) (hereinafter referred to as the imidization ratio) can be determined by the following method. First, the infrared absorption spectrum of the polymer is measured, and the absorption peak of the imide structure due to the polyimide (1780 cm －１ Near 1377 cm －１ The presence of an absorption peak (around 1470 cm) due to an aromatic ring was confirmed. －１ When the peak intensity at 1377 cm －１ Next, the polymer is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured. －１ When the peak intensity at 1377 cm －１ The peak intensity (Z) around the peak intensity Y is determined. The ratio of these peak intensities corresponds to the content of imide groups in the polymer before heat treatment, i.e., the imidization rate (%) (imidization rate = Y / Z × 100 (%)). The proportion of amic acid structures in polyimide resin (A) (hereinafter referred to as amic acid rate) can be determined by the following formula: Amic acid rate (%) = 100 - (esterification rate (%) + imidization rate (%)).

[0065] The polyimide resin (A) may contain a structure derived from another tetracarboxylic dianhydride in addition to the alicyclic tetracarboxylic dianhydride represented by formula (7), as long as the effect of the present invention, that is, pattern processing with high sensitivity without causing residue or peeling, is not impaired.

[0066] Specific examples of other tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)propane dianhydride, and 1,1-bis(2,3-dicarboxyphenyl)propane dianhydride. Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}- aromatic tetracarboxylic dianhydrides such as 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,2,3,4-cyclopentanetetracarboxylic dianhydride; and 1,2,4,5-cyclohexanetetracarboxylic dianhydride. Tetracarboxylic acid dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic dianhydride, 1,3,3a,4,5,Examples of suitable tetracarboxylic acid dianhydrides include, but are not limited to, 9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione and acid dianhydrides having the structure shown in the following formula (13), as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. Furthermore, two or more of these tetracarboxylic acid dianhydride components may be used in combination.

[0067]

[0068] R １０ is a direct bond, -SO ２ -, -O-, -S-, -CO-, -C(CF ３ ) ２ - or a hydrocarbon group having 1 to 20 carbon atoms, R １１ and R １２ each independently represents a hydrogen atom or a hydroxyl group.

[0069] Specific examples of diamines used as raw materials for the polyimide resin (A) include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)-2,2'-diamino-4-hydroxy ... (4-hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4' -diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-Diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-bis(2-aminoethoxy)ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-1 Examples of suitable diamine components include, but are not limited to, 76, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, and HT-1700 (all trade names, manufactured by HUNTSMAN Corporation), as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like, and diamines having structures represented by the following formulas (14) and (15). Furthermore, two or more of these diamine components may be used in combination.

[0070]

[0071] R １３ and R １６ are each independently a direct bond, —SO ２ -, -O-, -S-, -CO-, -C(CF ３ ) ２ - or a hydrocarbon group having 1 to 20 carbon atoms, R １４ , R １５ , R １７ , and R １８ each independently represents a hydrogen atom or a hydroxyl group.

[0072] The polyimide resin (A) preferably has a residue of a monoamine or an acid anhydride at at least one end of the main chain. Here, the monoamine or the acid anhydride is an end-capping agent. The use of the end-capping agent has the well-known effects of suppressing hydrolysis of the resin due to the acid end and suppressing deterioration of the quinone diazide compound, which is the photosensitizer, due to the amine end when the resin is made into a positive-tone photosensitive resin composition. In addition, it has the effect of enabling processing without leaving residues when using a commonly used 2.38% by mass TMAH aqueous solution as a developer.

[0073] Specific examples of monoamines used as end-capping agents include M-600, M-1000, M-2005, and M-2070 (all trade names, manufactured by HUNTSMAN Corporation), aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3-vinylaniline, 4-vinylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, and 1-carboxy-2-aminonaphthalene. Examples of compounds that can be used include carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these compounds may also be used.

[0074] Specific examples of acid anhydrides that can be used as end-capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, methacrylic anhydride, acrylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 4-phenylethynylphthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. Two or more of these may be used.

[0075] For the purpose of improving the folding endurance and chemical resistance of the cured resin obtained by heat-curing the resin composition, it is particularly preferable to use a monoamine or acid anhydride having at least one reactive unsaturated bond such as an alkenyl group or alkynyl group as the end-capping agent.

[0076] The monoamine having at least one reactive unsaturated bond such as an alkenyl group or an alkynyl group is not particularly limited, but examples thereof include 4-ethynylaniline, 3-ethynylaniline, 4-vinylaniline, and 3-vinylaniline.

[0077] The acid anhydride having at least one reactive unsaturated bond such as an alkenyl group or an alkynyl group is not particularly limited, and examples thereof include 5-norbornene-2,3-dicarboxylic acid anhydride, maleic acid anhydride, methacrylic acid anhydride, acrylic acid anhydride, 1,2,3,6-tetrahydrophthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, and 4-phenylethynylphthalic acid anhydride.

[0078] The reactive unsaturated bond refers to a chemically active unsaturated bond that serves as a reaction point with other compounds, such as a reaction point between reactive unsaturated bonds or a reaction point with a thermal crosslinking agent (C) described later.

[0079] In order to prevent peeling of the resin composition of the present invention after development, the content of fluorine atoms in the polyimide resin (A) is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less, relative to 100% by mass of the polyimide resin (A).

[0080] When a monoamine is used as the end-capping agent, its introduction ratio is preferably 1 mol% or more and 60 mol% or less, relative to 100 mol% of all amine compounds contained in the polyimide resin (A). By setting the introduction ratio of the monoamine to preferably 1 mol% or more, more preferably 5 mol% or more, the effect of reducing residue after development can be effectively obtained. Furthermore, by setting the introduction ratio of the monoamine to preferably 60 mol% or less, more preferably 50 mol% or less, the molecular weight of the polyimide resin (A) can be maintained high, and high chemical resistance and mechanical strength can be maintained. Here, the term "total amine compounds" refers to the total molar content of compounds having an amino group, such as monoamines, diamines, and triamines.

[0081] When an acid anhydride compound is used as the end-capping agent, the total introduction ratio thereof is preferably 1 mol part or more and 100 mol parts or less relative to 100 mol parts of all acid anhydride compounds contained in the polyimide resin (A). By setting the introduction ratio to preferably 1 mol part or more, more preferably 5 mol parts or more, the effect of reducing residue after development can be effectively obtained. On the other hand, by setting the introduction ratio to preferably 100 mol parts or less, more preferably 90 mol parts or less, the molecular weight of the polyimide resin (A) can be maintained high, and high chemical resistance and mechanical strength can be maintained.

[0082] The weight-average molecular weight of the polyimide resin (A), which can be determined in terms of polystyrene by gel permeation chromatography (GPC), is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more from the viewpoint of folding endurance of the cured product, while the weight-average molecular weight of the polyimide resin (A) is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 35,000 or less from the viewpoint of alkali solubility.

[0083] The integral molecular weight distribution curve of the polyimide resin (A) can be analyzed using GPC analysis software. The content of molecular weights of 1,000 or less determined from the integral molecular weight distribution curve (calculated as the area ratio of the integral molecular weight distribution curve) is preferably 1.0% or less, more preferably 0.9% or less, even more preferably 0.8% or less, and particularly preferably 0.7% or less, from the viewpoint of folding resistance of the cured product, and is preferably 0.1% or more from the viewpoint of storage stability of the resin composition.

[0084] The resin composition of the present invention may contain a resin other than the polyimide resin (A). Specific examples include polybenzoxazole, polybenzoxazole precursor, polyamide, acrylic polymer copolymerized with acrylic acid, novolak resin, resol resin, siloxane resin, polyhydroxystyrene resin, resins into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced, and copolymers thereof. Such resins are soluble in aqueous solutions of alkalis such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. By including these resins, the properties of each resin can be imparted without impairing the effect of the present invention, which is to enable highly sensitive pattern processing without causing residue or peeling.

[0085] <Photosensitive Compound (B)> The resin composition of the present invention contains a photosensitive compound (B). Examples of the photosensitive compound include a photoacid generator (B1) and a photopolymerization initiator (B2). The photoacid generator (B1) is a compound that generates an acid when irradiated with light, and the photopolymerization initiator (B2) is a compound that generates radicals by bond cleavage and / or reaction when exposed to light.

[0086] By including a photoacid generator (B1), acid is generated in the irradiated areas, increasing the solubility of the irradiated areas in an alkaline aqueous solution, thereby obtaining a positive relief pattern in which the irradiated areas are dissolved. Furthermore, by including a photoacid generator (B1) and an epoxy compound or an oxetane compound, the acid generated in the irradiated areas promotes the crosslinking reaction of the epoxy compound or oxetane compound, thereby obtaining a negative relief pattern in which the irradiated areas are insolubilized. Furthermore, by including a photopolymerization initiator (B2) and a radically polymerizable compound (described later), radical polymerization proceeds, rendering the exposed areas of the resin composition film insoluble in an alkaline developer, thereby forming a negative pattern.

[0087] Examples of the photoacid generator (B1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

[0088] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and / or a sulfonamide bond. Preferably, 50 mol% or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. In addition, it is preferable to contain two or more photoacid generators (B1), which allows for the production of a highly sensitive resin composition.

[0089] In the present invention, either a 5-naphthoquinone diazide sulfonyl ester compound or a 4-naphthoquinone diazide sulfonyl compound is preferably used as the quinone diazide compound. The compound may contain a naphthoquinone diazide sulfonyl ester compound having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or may contain a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

[0090] The quinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. The use of these quinone diazide compounds further improves resolution, sensitivity, and film retention.

[0091] Among the photoacid generators (B1), sulfonium salts, phosphonium salts, and diazonium salts are preferred because they appropriately stabilize the acid component generated by exposure. Of these, sulfonium salts are preferred. Furthermore, a sensitizer or the like may also be contained as needed.

[0092] In the present invention, the content of the photoacid generator (B1) is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the polyimide resin (A) from the viewpoint of achieving high sensitivity. Among these, the content of the quinone diazide compound is preferably 3 to 40 parts by mass. The total amount of the sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

[0093] Examples of the photopolymerization initiator (B2) include, for example, benzyl ketal photopolymerization initiators, α-hydroxyketone photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, acridine photopolymerization initiators, titanocene photopolymerization initiators, benzophenone photopolymerization initiators, acetophenone photopolymerization initiators, aromatic ketoester photopolymerization initiators, and benzoic acid ester photopolymerization initiators. From the viewpoint of improving sensitivity during exposure, α-hydroxyketone photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, acridine photopolymerization initiators, and benzophenone photopolymerization initiators are more preferred, and α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime ester photopolymerization initiators are even more preferred.

[0094] In the present invention, the content of the photopolymerization initiator (B2) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the total of the polyimide resin (A) and the radically polymerizable compound described below. When the content is within the above range, the sensitivity during exposure can be improved. On the other hand, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. When the content is within the above range, the resolution after development can be improved and a pattern shape with a low taper can be obtained.

[0095] <Thermal Crosslinking Agent (C)> The resin composition of the present invention preferably contains a thermal crosslinking agent. A thermal crosslinking agent is a compound that reacts with other molecules by heat to form chemical bonds, and refers to a compound having at least two thermally reactive functional groups in the molecule. The thermal crosslinking agent (C) crosslinks the polyimide resin (A) or other additive components, and can improve the chemical resistance and heat resistance of the cured product.

[0096] Preferred examples of the thermally reactive functional group used in the present invention include a methylol group, an alkoxymethyl group, an epoxy group, and an oxetanyl group.

[0097] Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups as the thermally reactive functional group include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, and TML-BPA. , TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NI Examples of such compounds include "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.), and each of these compounds is available from the respective companies listed above.

[0098] Preferred examples of compounds having at least two epoxy groups or oxetanyl groups as thermally reactive functional groups include those having two epoxy groups in one molecule, those having three or more epoxy groups, etc. Examples of compounds having two epoxy groups as thermally reactive functional groups in one molecule include "Epicoat" (registered trademark) 807, "Epicoat" (registered trademark) 828, "Epicoat" (registered trademark) 1002, "Epicoat" (registered trademark) 1750, "Epicoat" (registered trademark) 1007, YX8100-BH30, E1256, E4250, E4275 (all trade names, manufactured by Japan Epoxy Co., Ltd.), and "Epiclon" (registered trademark). EXA-4880, "Epicron" (registered trademark) EXA-4822, "Epicron" (registered trademark) EXA-9583, HP4032 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), "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) 4000, "Epolite" (registered trademark) 3002 (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, "Denacol" (registered trademark) EX-214L, "Denacol" (registered trademark) EX-216L, "Denacol" (registered trademark) E Examples of such compounds include X-252, "Denacol" (registered trademark) EX-850L (all trade names, manufactured by Nagase ChemteX Corporation), GAN, GOT (all trade names, manufactured by Nippon Kayaku Co., Ltd.), "Celloxide" (registered trademark) 2021P (trade name, manufactured by Daicel Corporation), "Rikaresin" (registered trademark) DME-100, "Rikaresin" (registered trademark) BEO-60E (all trade names, manufactured by New Japan Chemical Co., Ltd.), and each of these compounds is available from the respective companies.Examples of compounds having three or more epoxy groups as thermally reactive functional groups include "TECHMORE" (registered trademark) VG3101L (trade name, manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark) S, "TEPIC" (registered trademark) G, "TEPIC" (registered trademark) P (all trade names, manufactured by Nissan Chemical Industries, Ltd.), "Epiclon" (registered trademark) N660, "Epiclon" (registered trademark) N695, HP7200 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), "Denacol" (registered trademark) EX-321L (trade name, manufactured by Nagase ChemteX Corporation), NC6000, EPPN502H, N C3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EHPE-3150 (trade name, manufactured by Daicel Corporation), and the like. Compounds having two or more oxetanyl groups as thermally reactive functional groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (trade name, manufactured by Toagosei Co., Ltd.), "Etanacol" (registered trademark) OXBP, "Etanacol" (registered trademark) OXTP (trade name, manufactured by Ube Industries, Ltd.), and the like, each of which is available from the respective companies.

[0099] Examples of the structure that serves as the base for bonding the thermally reactive functional group of the thermal crosslinking agent (C) include an isocyanuric ring structure, an alicyclic structure, and an aliphatic structure.

[0100] The thermal crosslinking agent (C) used in the present invention preferably contains one or more thermal crosslinking agents selected from the group consisting of an isocyanuric ring structure-containing epoxy thermal crosslinking agent, which is a compound containing two or more epoxy groups in an isocyanuric ring structure; an alicyclic epoxy thermal crosslinking agent, which is a compound containing two or more epoxy groups in an alicyclic structure; and an aliphatic epoxy thermal crosslinking agent, which is a compound containing two or more epoxy groups in an aliphatic structure. These epoxy thermal crosslinking agents have a structure free of aromatic rings, which appropriately enhances solubility in alkaline developers and enables high-sensitivity pattern processing without residue or peeling. Furthermore, the flexible structure of the crosslinked moiety enhances the fluidity of the resin composition during thermal curing, resulting in superior planarization. Furthermore, decomposition due to exposure to heat or ultraviolet light is suppressed, which is also preferred in terms of demonstrating high bending resistance. The isocyanuric ring structure-containing epoxy thermal crosslinking agent is an epoxy thermal crosslinking agent containing an isocyanuric ring structure in the compound structure. Alicyclic epoxy thermal crosslinkers are epoxy thermal crosslinkers having one or more alicyclic structures having 3 to 12 carbon atoms, which may contain a heteroelement or a branched structure, in a compound structure other than an ethylene oxide structure. Aliphatic epoxy thermal crosslinkers are epoxy thermal crosslinkers having a structure having 3 to 24 carbon atoms, which is not an alicyclic structure, which may contain a heteroelement or a branched structure, in a compound structure other than an ethylene oxide structure. Furthermore, epoxy thermal crosslinkers containing an isocyanuric ring and an alicyclic structure and / or an aliphatic structure are classified herein as isocyanuric ring structure-containing epoxy thermal crosslinkers. Epoxy thermal crosslinkers containing no isocyanuric ring and an alicyclic structure and an aliphatic structure are classified herein as alicyclic epoxy thermal crosslinkers.

[0101] From the viewpoint of enhancing the crosslinking properties of the resin, it is preferable that the isocyanuric ring structure-containing epoxy thermal crosslinking agent, alicyclic epoxy thermal crosslinking agent, and aliphatic epoxy thermal crosslinking agent have two or more epoxy groups in the molecule.

[0102] Examples of the isocyanuric ring structure-containing epoxy thermal crosslinking agent include "TEPIC" (registered trademark)-S, "TEPIC"-G, "TEPIC"-L, and "TEPIC"-VL (all trade names, manufactured by Nissan Chemical Industries, Ltd.), and MA-DGIC (trade name, manufactured by Shikoku Chemical Industries, Ltd.). Examples of alicyclic epoxy thermal crosslinking agents include "Celloxide" (registered trademark) 2021P, "Celloxide" 2081, "Celloxide" 8000, and "Celloxide" 8010 (trade names, manufactured by Daicel Corporation), "Denacol" (registered trademark) EX-252 (trade name, manufactured by Nagase ChemteX Corporation), "Epocalic" (registered trademark) THI-DE, "Epocalic" DE-102, and "Epocalic" DE-103 (trade names, manufactured by ENEOS Corporation), and "Shofree" (registered trademark) CDMDG (trade name, manufactured by Resonac Corporation). Examples of aliphatic epoxy thermal crosslinking agents include "Denacol" Examples of suitable thermal crosslinking agents include "DENACOL" (registered trademark) EX-614B, "DENACOL" EX-313, "DENACOL" EX-512, "DENACOL" EX-321L, "DENACOL" EX-810, "DENACOL" EX-861, and "DENACOL" EX-211 (all trade names, manufactured by Nagase ChemteX Corporation), EPOGOSE" (registered trademark) BD, "EPOGOSE" NPG, and "EPOGOSE" HD (trade names, manufactured by Yokkaichi Synthetic Co., Ltd.), and "SHOFREE" (registered trademark) PETG (trade name, manufactured by Resonac Corporation), each of which is available from the respective companies. Two or more types of thermal crosslinking agents may be used in combination.

[0103] The content of the thermal crosslinking agent (C) in the resin composition is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the polyimide resin (A), from the viewpoint of enabling pattern processing with high sensitivity without causing residue or peeling. From the viewpoint of maintaining heat resistance, the content 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.

[0104] The resin composition of the present invention may contain a solvent (D). The resin composition of the present invention preferably contains, as the solvent (D), a solvent (D1) represented by formula (11) and / or a solvent represented by formula (12).

[0105]

[0106] (In formulas (11) and (12), a plurality of R ２２ each independently represents an alkyl group having 1 to 6 carbon atoms; R ２３ represents an alkyl group having 2 to 6 carbon atoms.) The inclusion of solvent (D1) promotes the ring-closure reaction of polyimide resin (A), thereby improving the mechanical properties and chemical resistance of the cured product obtained by curing the photosensitive resin composition. Furthermore, since the solvent (D1) strongly interacts with the polyimide resin (A) component and the substrate, the inclusion of solvent (D1) can improve development adhesion. In addition, since the solvent (D1) easily solvates with polyimide resin (A), it can suppress changes such as aggregation that tend to occur during storage of the resin composition, improving storage stability.

[0107] The β-alkoxypropionamide, which is a compound represented by formula (11), is preferably 3-methoxy-N,N-dimethylpropanamide (hereinafter, MPA) or 3-butoxy-N,N-dimethylpropanamide, from the viewpoint of improving development adhesion and storage stability of the resin composition.

[0108] The compound represented by formula (12) is preferably N,N-dimethylisobutyramide, N,N-dimethylpropionamide (hereinafter, DMPA) from the viewpoint of improving development adhesion and storage stability of the resin composition.

[0109] In the present invention, the total content of the compound represented by formula (11) and the compound represented by formula (12) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the polyimide resin (A). On the other hand, from the viewpoint of being able to form a desired patterned film when used as a developed film, the total content is preferably 200 parts by mass or less, more preferably 100 parts by mass or less.

[0110] The resin composition of the present invention preferably contains, as the solvent (D), a solvent (D2) that is a compound having a hydroxyl group and having a boiling point at atmospheric pressure of 100° C. or more and 200° C. or less. By containing the solvent (D2), it is possible to improve developability, suppress the generation of development residues, and improve sensitivity.

[0111] Specific examples of the solvent (D2) include, but are not limited to, propylene glycol monomethyl ether (hereinafter, PGME; boiling point 120°C), methyl lactate (boiling point 145°C), ethyl lactate (boiling point 154°C), propyl lactate (boiling point 169°C), 1-butanol (boiling point 117°C), 1-pentanol (boiling point 138°C), 1-hexanol (boiling point 157°C), cyclohexanol (boiling point 161°C), 3-methoxybutanol (boiling point 161°C), ethylene glycol monomethyl ether (boiling point 124°C), diacetone alcohol (boiling point 166°C), tetrahydrofurfuryl alcohol (boiling point 176°C), and diethylene glycol monomethyl ether (boiling point 194°C).

[0112] The content of the solvent (D2) contained in the resin composition of the present invention is preferably 5 to 3,000 parts by mass, more preferably 10 to 1,000 parts by mass, per 100 parts by mass of the total amount of the resin (A).

[0113] The resin composition of the present invention contains both the solvent (D1) and the solvent (D2) as the solvent (D), and when the content of the solvent (D1) in the resin composition is X (parts by mass) and the content of the solvent (D2) is Y (parts by mass), the content ratio Y / X is preferably 1 or more and 1000 or less, and more preferably 2 or more and 900 or less. When the ratio Y / X is within the above range, it is possible to satisfy all of the properties of improved development adhesion, suppression of development residues, improved storage stability of the resin composition, and improved sensitivity.

[0114] The photosensitive resin composition of the present invention may contain a solvent (D3) other than the solvent (D1) and the solvent (D2). Examples of the solvent (D3) include: ethers such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl lactate, methyl levulinate, ethyl levulinate, propyl levulinate, and butyl levulinate; alcohols such as methanol, ethanol, isopropanol, α-terpineol, β-terpineol, and γ-terpineol, which have a boiling point at atmospheric pressure of less than 100°C or more than 200°C; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, and cyclopentanone; Examples of suitable solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidone, and dihydrolevoglucosenone (Cyrene, manufactured by Circa), and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be used.

[0115] The content of the solvent (D3) is preferably 70 parts by mass or more, more preferably 100 parts by mass or more, relative to 100 parts by mass of the polyimide resin (A) in terms of resin solubility, and is preferably 2,500 parts by mass or less, more preferably 2,000 parts by mass or less, in terms of obtaining an appropriate film thickness.

[0116] The resin composition of the present invention may contain a radically polymerizable compound. In the present invention, the radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule. During exposure, radicals generated from the photopolymerization initiator (B2) cause radical polymerization of the radically polymerizable compound to proceed, and the exposed portion of the resin composition film becomes insoluble in an alkaline developer, thereby forming a negative pattern.

[0117] The inclusion of a radical polymerizable compound accelerates UV curing during exposure, improving sensitivity during exposure, and also improves crosslink density after thermal curing, thereby improving the hardness of the cured product.

[0118] The radical polymerizable compound in the present invention is preferably a compound having a (meth)acrylic group, which facilitates radical polymerization. From the viewpoint of improving sensitivity during exposure and improving hardness of the cured product, a compound having two or more (meth)acrylic groups in the molecule is more preferred. From the viewpoint of improving sensitivity during exposure and improving hardness of the cured product, the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol.

[0119] In the present invention, the content of the radical polymerizable compound is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, based on 100 parts by mass of the total of the polyimide resin (A) and the radical polymerizable compound. When the content is within the above range, the sensitivity during exposure can be improved and a pattern shape with a low taper can be obtained. On the other hand, the content is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less. When the content is within the above range, the heat resistance of the cured product can be improved and a pattern shape with a low taper can be obtained.

[0120] In addition to the above-mentioned components, the resin composition of the present invention may contain, if necessary, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, and a colorant.

[0121] Next, a method for producing the resin composition of the present invention will be described. For example, the resin composition can be obtained by dissolving or dispersing the polyimide resin (A) and the photosensitive compound (B), and, if necessary, a thermal crosslinking agent (C), an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, a colorant, etc., in an organic solvent.

[0122] Methods for dissolving or dispersing the resin composition in a solvent 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 room temperature to 80° C. The order in which the components are dissolved is not particularly limited, and examples include a method in which the components are dissolved in order starting with the least soluble compound.

[0123] 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.

[0124] The cured product of the present invention is obtained by curing the resin composition. To cure the resin composition, the resin composition may be heated. Heat curing can remove components with low heat resistance, thereby improving the heat resistance and chemical resistance of the cured product. The polyimide resin (A) can form imide rings by heat curing, thereby improving heat resistance and chemical resistance. Furthermore, when a thermal crosslinking agent (C) is contained, heat curing can promote a thermal crosslinking reaction, thereby improving 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 product. From the viewpoint of improving the toughness of the cured product, the heat curing temperature 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 product. Furthermore, from the viewpoint of improving the toughness of the cured product, it is preferably 3 hours or shorter. 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.

[0125] Next, a method for producing a cured product from the resin composition of the present invention will be described. More specifically, a cured product can be produced by applying the resin composition to a substrate to form a resin film, drying the resin film, and heat-treating the resin film. At this time, the portion of the polyimide resin (A) having an imide precursor structure can close into an imide ring. Furthermore, if the polyimide resin (A) has reactive unsaturated bonds, it can also crosslink with itself to extend the molecular chain. Furthermore, if a thermal crosslinking agent (C) is contained, thermal crosslinking can be performed between the thermal crosslinking agents (C) or between the thermal crosslinking agent (C) and the polyimide resin (A).

[0126] First, a resin composition is applied to a substrate to form a resin film. Examples of application methods include spin coating, slit coating, dip coating, spray coating, and printing. Among these, slit coating is preferred because it allows application 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, approximately 1 / 5 to 1 / 10 of that required for spin coating. Examples of slit coaters used for application 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 "Inline Slit Coater" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC Series" manufactured by Hirata Corporation. When a slit coater is used, 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 solid content and viscosity of the resin composition, but the resin is usually coated so that the film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0127] The substrate may be a wafer of glass, silicon, ceramics, gallium arsenide, or the like, or a substrate on which metal is formed as an electrode or wiring, but is not limited to these.

[0128] Next, particularly when the resin composition contains a solvent, the resin film provided on the substrate is dried, i.e., volatile components that volatilize at temperatures up to the drying temperature are removed. Known drying methods can be used, such as methods using a hot plate, oven, or infrared radiation. Alternatively, the substrate on which the resin film is 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.

[0129] A cured product can be obtained by heat-curing the resin film. Heat-curing can remove components with low heat resistance, thereby further improving 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 product. From the viewpoint of improving the toughness of the cured product, the heat-curing temperature 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. From the viewpoint of improving the heat resistance of the cured product, the heat-curing time is preferably 30 minutes or longer. Furthermore, from the viewpoint of improving the toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat-treating at 150°C and 260°C for 60 minutes each, or a method of heat-treating while linearly increasing the temperature from room temperature to 270°C over 2 hours, can be mentioned.

[0130] Next, a method for producing a patterned cured product from the resin composition of the present invention will be described. More specifically, the resin composition is applied to a substrate to form a resin film, the resin film is dried, the resin film is exposed to light, the exposed resin film is developed, and the developed resin film is heat-treated to produce a cured product. The application step, drying step, and heat-treatment step are as described above, and the resin film exposure step and development step will be described below.

[0131] 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.

[0132] 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 resin film has positive photosensitivity, the exposed area dissolves in the developer. When the resin film has negative photosensitivity, the exposed area hardens and becomes insoluble in the developer.

[0133] The exposed resin film is then developed. In the case of a positive-tone film, the exposed areas are removed with a developer to form the desired pattern. The developer is preferably an aqueous solution of an alkaline compound such as TMAH, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. These alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, or dimethylacrylamide; alcohols such as methanol, ethanol, or isopropanol; esters such as ethyl lactate or propylene glycol monomethyl ether acetate; or ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone. Among these developers, a 2.38% by mass aqueous solution of TMAH is preferably used, which is generally used. Examples of the developing method include spray, paddle, immersion, and ultrasonic methods.

[0134] 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.

[0135] The cured product formed from the resin composition of the present invention can be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, specifically, for example, a planarizing layer in a liquid crystal display device, a planarizing layer and / or a pixel dividing layer in an organic EL display device, etc. The following description will be given taking an organic EL display device as an example.

[0136] The organic EL display device of the present invention includes the cured product. Specifically, the organic EL display device preferably has a substrate on which a driving circuit, a planarization layer, a first electrode, a pixel division layer, an organic EL layer (light-emitting layer), and a second electrode are disposed, with the planarization layer and / or the pixel division layer comprising the cured product. Taking an active matrix display device as an example, a substrate such as glass or a resin film has a thin-film transistor (hereinafter sometimes referred to as "TFT") as a driving circuit, wiring located on the sides of the TFT and connected to the TFT, a planarization layer on top of the driving circuit to cover the unevenness, and an organic EL layer on the planarization layer. The organic EL layer and the wiring are connected via contact holes and the first electrode formed in the planarization layer. In particular, flexible organic EL display devices have become mainstream in recent years, and an organic EL display device in which the substrate carrying the driving circuit is made of a resin film is preferred.

[0137] The semiconductor device of the present invention also includes the cured product. In this case, the cured product can be used as an insulating film or protective film constituting a semiconductor device (electronic component). Examples of semiconductor devices (electronic components) include active components such as transistors, diodes, integrated circuits, and memories, and passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices. Specific examples of cured products suitable for electronic components include passivation films for semiconductors, surface protective films for semiconductor elements and TFTs, interlayer insulating films in multilayer wiring for high-density packaging with 2 to 10 layers, and insulating and protective films for touch panel displays. However, the cured product is not limited to these and can have a variety of structures. The surface of the substrate on which the cured product is formed can be appropriately selected depending on the application and process, and examples include silicon, ceramics, metal, glass, and epoxy resin. Multiple materials may be arranged on the same surface. Examples of electronic devices having a surface protective film or interlayer insulating film comprising the cured product of the present invention include magnetoresistive memories (hereinafter, MRAMs) with low heat resistance. In other words, the cured product of the present invention is suitable as a surface protective film for MRAMs. In addition to MRAM, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM), which are promising next-generation memories, are also likely to use new materials with lower heat resistance than conventional memories. Therefore, the cured product of the present invention is also suitable for use as a surface protection film for these memories. It is also suitable for use in fan-out wafer-level packages (hereinafter referred to as fan-out WLP). Fan-out WLP is a semiconductor package in which an extension section is provided around the periphery of a semiconductor chip using an encapsulating resin such as epoxy resin, rewiring is performed from the electrodes on the semiconductor chip to the extension section, and solder balls are also mounted on the extension section to ensure the required number of terminals. In fan-out WLP, wiring is installed so as to straddle the boundary formed by the main surface of the semiconductor chip and the main surface of the encapsulating resin. That is, an interlayer insulating film is formed on a base material made of two or more materials, namely, a semiconductor chip provided with metal wiring and a sealing resin, and wiring is then formed on the interlayer insulating film.In addition, in a semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is provided so as to straddle the boundary between the main surface of the semiconductor chip and the main surface of the printed circuit board. In this embodiment, an interlayer insulating film is formed on a substrate made of two or more materials, and wiring is formed on the interlayer insulating film. The cured product obtained by curing the resin composition of the present invention has high adhesion to a semiconductor chip provided with metal wiring and also has high adhesion to sealing resins such as epoxy resins, making it suitable for use as an interlayer insulating film provided on a substrate made of two or more materials.

[0138] The present invention will be described below with reference to examples, but the present invention should not be construed as being limited to these examples. First, the evaluation method will be described. Unless otherwise specified, the evaluation was performed with n=1.

[0139] [Evaluation Method] (1) Ratio of Amic Acid Ester Structures in Polyimide Resin (Esterification Rate) Using a nuclear magnetic resonance (NMR) device (EX-270 manufactured by JEOL Ltd.), a mixed solution of 10 mg of the polyimide resin obtained in each Synthesis Example and 0.8 g of deuterated dimethyl sulfoxide was measured. １ H-NMR was measured, and the integral value (U) of the peak derived from the methyl protons of the carboxylic acid alkyl ester was determined, assuming that the integral value of the peak derived from the aromatic protons of the polyimide resin was 100. Next, from the ratio of the monomers constituting the polyimide resin, the integral value (V) of the peak derived from the methyl protons of the carboxylic acid alkyl ester was calculated, assuming that the integral value of the peak derived from the aromatic protons at an esterification rate of 100% was 100. Using the thus determined U and V, the esterification rate (%) was calculated according to the following formula: Esterification rate (%) = U / V × 100.

[0140] (2) Ratio of imide structure in polyimide resin (imidization ratio) A solution prepared by dissolving 4.5 g of the polyimide resin obtained in each synthesis example in 10.5 g of γ-butyrolactone was spin-coated onto a silicon wafer and dried at 120°C for 3 minutes. Next, the infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (FT-730 manufactured by Horiba, Ltd.). The absorption peak (1780 cm) of the imide structure due to polyimide was measured. －１ Near 1377 cm －１ The presence of an absorption peak (around 1470 cm) due to an aromatic ring was confirmed. －１ When the peak intensity at 1377 cm －１ Next, the coating film was heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again. －１ When the peak intensity at 1377 cm －１ The peak intensity (Z) around the peak was measured, and the imidization rate (%) was calculated as the peak intensity ratio Y / Z×100 (%).

[0141] (3) Proportion of Amic Acid Structure in Polyimide Resin (Amic Acid Ratio) The molar proportion of amic acid structures in the polyimide resin obtained in each Synthesis Example (hereinafter referred to as amic acid ratio) was calculated by the following formula: Amic acid ratio (%) = 100 - (esterification ratio (%) + imidization ratio (%)).

[0142] (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.

[0143] (5) Sensitivity The resin composition was applied by spin coating onto an 8-inch SiNx-coated silicon wafer 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 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 10 μm square opening pattern. ２ in the range of 5 mJ / cm ２Thereafter, using the ACT-8, the film was treated with a 2.38% by mass aqueous solution of TMAH as a developer until the thickness of the unexposed area reached 2.5 μm, and then rinsed with pure water and spun off to dry, thereby obtaining a pattern.

[0144] The obtained pattern was observed at a magnification of 50 times using a microscope MX61 (manufactured by Olympus Corporation), and the minimum exposure dose (ExA) (unit: mJ / cm) at which the opening diameter reached 10 μm was determined. ２ The smaller the minimum exposure amount, the higher the sensitivity.

[0145] ExA is 100 mJ / cm ２ In the following cases, it is "5 points", 105 mJ / cm ２ 130mJ / cm or more ２ In the following cases, it is "4 points", 135 mJ / cm ２ 160mJ / cm or more ２ In the following cases, "3 points" is given, and 165 mJ / cm ２ More than 190mJ / cm ２ In the following cases, "2 points" is given, and 195 mJ / cm ２ Anything above this was judged as "1 point," and anything above 3 points was considered a pass.

[0146] (6) Adhesion during Development A pattern was obtained in the same manner as in (5), except that the mask was changed to one having a 10 μm square light-shielding pattern.

[0147] The obtained pattern was observed at 10 points on the dot pattern at a magnification of 50 times using a microscope MX61 (manufactured by Olympus Corporation), and the minimum exposure dose (ExB) (unit: mJ / cm) at which peeling occurred in two or more points was determined. ２ The larger the positive value of the exposure dose difference ExB-ExA between the minimum exposure dose ExB in (6) and the minimum exposure dose ExA in (5), the larger the process margin for development adhesion relative to the exposure dose, and the better the development adhesion can be said to be.

[0148] ExB-ExA is 20 mJ / cm ２ In the above cases, it is "5 points", 15 mJ / cm ２ In the case of "4 points", 10 mJ / cm ２ In the case of "3 points", 5 mJ / cm ２ In the case of "2 points", 0 mJ / cm ２The following cases were judged as "1 point", and 3 points or more was considered a pass.

[0149] (7) Development Residue The pattern obtained in (5) was observed at a magnification of 50 times using a microscope MX61 (manufactured by Olympus Corporation), and the minimum exposure dose ExC (unit: mJ / cm) at which no residual film or residue was observed in the opening was determined. ２ The larger the negative value of the exposure dose difference ExC-ExA between the minimum exposure dose ExC in (7) and the minimum exposure dose ExA in (5), the larger the process margin of development residue relative to the exposure dose, which can be said to be better from the viewpoint of development residue.

[0150] ExC-ExA is -20 mJ / cm ２ In the following cases, it is "5 points", -15 mJ / cm ２ In the case of "4 points", -10 mJ / cm ２ In the case of "3 points", -5 mJ / cm ２ In the case of "2 points", 0 mJ / cm ２ Anything above this was judged as "1 point," and anything above 3 points was considered a pass.

[0151] In Table 3, ">0" means that a residual film or residue was observed at the minimum exposure (ExA) at which the opening diameter reached 10 μm, and is judged to be poor as development residue.

[0152] (8) Storage Stability (Change in Sensitivity After Storage) The resin compositions obtained in each of the Examples and Comparative Examples were left to stand at 23°C and 45% RH for 5 days, and then the sensitivity was evaluated in the same manner as in (5) to determine the sensitivity. The sensitivity before storage was measured as (ExA) (unit: mJ / cm ２ ), and the sensitivity after standing was (ExD) (unit: mJ / cm ２ ), the smaller the absolute value of the exposure dose difference ExD - ExA, the smaller the change in sensitivity during storage, and therefore the better the storage stability. ２ In the following cases, it is "5 points", 5 mJ / cm ２ Greater than 10 mJ / cm ２ In the following cases, "4 points" is given, and 10 mJ / cm ２ Greater than 15 mJ / cm ２ In the following cases, "3 points" is given, and 15 mJ / cm ２ Greater than 20 mJ / cm２ In the following cases, "2 points" is given, and 20 mJ / cm ２ If it was greater than this, it was judged as "1 point", and if it was 3 points or more, it was judged as passing.

[0153] [Synthesis Examples] Synthesis Example 1 Synthesis of Acid Dianhydride Compound (AD-1) 51.7 g (0.20 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane was dissolved in dehydrated acetone, and 34.8 g (0.60 mol) of propylene oxide was added. The mixture was cooled to -15°C. To this solution, a solution of 95.3 g (0.44 mol) of hydrogenated trimellitic anhydride chloride dissolved in dehydrated acetone was added dropwise. After the addition was completed, the mixture was reacted at -15°C for 4 hours and then returned to room temperature. The acetone was removed by distillation using an evaporator, and the resulting precipitate was filtered. The excess hydrogenated trimellitic anhydride chloride was dissolved and removed using toluene and hexane. The resulting mixture was vacuum dried at 80°C for 12 hours to obtain an acid dianhydride (hereinafter referred to as AD-1) represented by the following formula:

[0154]

[0155] Synthesis Example 2 Synthesis of Acid Dianhydride Compound (AD-2) An acid dianhydride represented by the following formula (hereinafter, AD-2) was obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane was changed to 73.3 g (0.20 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0156]

[0157] Synthesis Example 20: Synthesis of diamine compound (DAP-B) 26.70 g (0.086 mol) of BisP-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol, manufactured by Honshu Chemical Industry Co., Ltd.) and 100 ml of glacial acetic acid were charged into a 500 ml four-neck flask equipped with a stirrer, thermocouple, and dropping funnel, and the mixture was stirred. The internal temperature was raised to 50°C in a water bath. 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour, followed by ice cooling to lower the internal temperature to 13°C, and then 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was continued for 3 hours, and the precipitated yellow crystals were filtered, washed successively with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain the dinitro form.

[0158] Next, 54.06 g (0.135 mol) of the dinitro compound, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were placed in a 2 L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and the mixture was stirred under ice cooling. 0.9 g of 5% palladium-carbon (Wako Pure Chemical Industries, Ltd.) suspended in 30 ml of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 ml of ethanol. All of the solvent was removed by heating under reduced pressure, and the residue was washed with 75 ml of ice-cold ethanol, filtered, and then washed with 75 ml of deionized water and 150 ml of diethyl ether, followed by drying under reduced pressure, to obtain the diamine (DAP-B) represented by the following formula:

[0159]

[0160] Synthesis Example 21 Synthesis of diamine compound (DAP-C) A dinitro compound was synthesized using 23.25 g (0.086 mol) of 4,4'-(1,3-dimethylbutylidene)diphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.), and a diamine (DAP-C) represented by the following formula was obtained in the same manner as in Synthesis Example 20, except that 48.65 g (0.135 mol) of the dinitro compound was used.

[0161]

[0162] Synthesis Example 22 Synthesis of acid dianhydride compound (AD-3) An acid dianhydride represented by the following formula (hereinafter, AD-3) was obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane was changed to 68.1 g (0.20 mol) of the diamine (DAP-B) obtained in Synthesis Example 20.

[0163]

[0164] Synthesis Example 23: Synthesis of acid dianhydride compound (AD-4) An acid dianhydride represented by the following formula (hereinafter, AD-4) was obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane was changed to 60.1 g (0.20 mol) of the diamine (DAP-C) obtained in Synthesis Example 21.

[0165]

[0166] Synthesis Example 40 Synthesis of acid dianhydride compound (AD-5) An acid dianhydride represented by the following formula (hereinafter, AD-5) was obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane was changed to 42.6 g (0.20 mol) of 4,6-diaminoresorcinol dihydrochloride.

[0167]

[0168] Synthesis Example 3 Synthesis of Diamine Compound (DA-1) 164.8 g (0.45 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 900 mL of acetone and 156.8 g (2.7 mol) of propylene oxide, and the solution was cooled to −15°C. A solution of 183.7 g (0.99 mol) of 3-nitrobenzoyl chloride dissolved in 900 mL of acetone was added dropwise to the solution. After the dropwise addition was completed, the mixture was reacted at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and dried in vacuo at 50°C.

[0169] 270 g of the solid was placed in a 3 L stainless steel autoclave and dispersed in 2400 mL of methyl cellosolve, and 5 g of 5% palladium-carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After 2 hours, the reaction was terminated after confirming that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a diamine compound represented by the following formula (hereinafter referred to as DA-1).

[0170]

[0171] Synthesis Example 4 Synthesis of Polyimide Resin (A-1) Under a dry nitrogen stream, 16.42 g (0.04 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter referred to as BAPP) as a diamine compound and 2.18 g (0.02 mol) of 3-aminophenol as an end-capping agent were dissolved in 200 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). To this was added 30.9 g (0.05 mol) of the acid dianhydride AD-1 obtained in Synthesis Example 1 along with 20 g of NMP, and the mixture was reacted at 20°C for 1 hour and then at 50°C for 2 hours. Thereafter, 14.30 g (0.12 mol) of N,N-dimethylformamide dimethyl acetal (hereinafter referred to as DMFDMA) was added, and the mixture was stirred at 50°C for 3 hours. 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 a washing operation of adding 5 L of water and filtering to collect the precipitate was repeated three times. The precipitate was then dried in a vacuum dryer at 80°C for 24 hours to obtain a powder of polyimide resin (A-1).

[0172] Synthesis Example 5 Synthesis of Polyimide Resin (A-2) A powder of polyimide resin (A-2) was obtained in the same manner as in Synthesis Example 4, except that the amount of DMFDMA added was changed to 11.92 g (0.10 mol).

[0173] Synthesis Example 6 Synthesis of Polyimide Resin (A-3) A powder of polyimide resin (A-3) was obtained in the same manner as in Synthesis Example 4, except that the amount of DMFDMA added was changed to 9.53 g (0.08 mol).

[0174] Synthesis Example 7 Synthesis of Polyimide Resin (A-4) A powder of polyimide resin (A-4) was obtained in the same manner as in Synthesis Example 4, except that the amount of DMFDMA added was changed to 7.15 g (0.06 mol).

[0175] Synthesis Example 8 Synthesis of Polyimide Resin (A-5) A powder of polyimide resin (A-5) was obtained in the same manner as in Synthesis Example 4, except that the amount of DMFDMA added was changed to 4.77 g (0.04 mol).

[0176] Synthesis Example 9 Synthesis of Polyimide Resin (A-6) Powder of polyimide resin (A-6) was obtained in the same manner as in Synthesis Example 4, except that DMFDMA was not added.

[0177] Synthesis Example 10 Synthesis of Polyimide Resin (A-7) Under a dry nitrogen stream, 16.42 g (0.04 mol) of BAPP as a diamine compound and 2.18 g (0.02 mol) of 3-aminophenol as an end-capping agent were dissolved in 200 g of NMP. 30.9 g (0.05 mol) of AD-1 as the acid dianhydride obtained in Synthesis Example 1 was added together with 20 g of NMP, and the mixture was reacted at 20°C for 1 hour, then at 50°C for 2 hours, and then at 110°C for 2 hours. After cooling the solution to room temperature, 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 performed three times. After that, the mixture was dried in a vacuum dryer at 80°C for 24 hours to obtain a powder of polyimide resin (A-7).

[0178] Synthesis Example 11 Synthesis of Polyimide Resin (A-8) Powder of polyimide resin (A-8) was obtained in the same manner as in Synthesis Example 10, except that the reaction time was changed from 2 hours at 110°C to 2 hours at 140°C.

[0179] Synthesis Example 12 Synthesis of Polyimide Resin (A-9) Powder of polyimide resin (A-9) was obtained in the same manner as in Synthesis Example 10, except that the reaction time was changed from 2 hours at 110°C to 2 hours at 160°C.

[0180] Synthesis Example 13 Synthesis of Polyimide Resin (A-10) Powder of polyimide resin (A-10) was obtained in the same manner as in Synthesis Example 10, except that the reaction time was changed from 2 hours at 110°C to 2 hours at 180°C.

[0181] Synthesis Example 14 Synthesis of Polyimide Resin (A-11) Powder of polyimide resin (A-11) was obtained in the same manner as in Synthesis Example 13, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-1.

[0182] Synthesis Examples 15 to 19 Synthesis of Polyimide Resins (A-12) to (A-16) Powders of polyimide resins (A-12) to (A-16) were obtained in the same manner as in Synthesis Example 5, except that the acid dianhydrides, diamines, and end-capping agents used were replaced as shown in Table 1-1.

[0183] Synthesis Example 24 Powder of polyimide resin (A-17) was obtained in the same manner as in Synthesis Example 4, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0184] Synthesis Example 25 Powder of polyimide resin (A-18) was obtained in the same manner as in Synthesis Example 5, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0185] Synthesis Example 26 Powder of polyimide resin (A-19) was obtained in the same manner as in Synthesis Example 6, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0186] Synthesis Example 27 Powder of polyimide resin (A-20) was obtained in the same manner as in Synthesis Example 7, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0187] Synthesis Example 28 Powder of polyimide resin (A-21) was obtained in the same manner as in Synthesis Example 8, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0188] Synthesis Example 29 Powder of polyimide resin (A-22) was obtained in the same manner as in Synthesis Example 9, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0189] Synthesis Example 30 Powder of polyimide resin (A-23) was obtained in the same manner as in Synthesis Example 10, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0190] Synthesis Example 31 Powder of polyimide resin (A-24) was obtained in the same manner as in Synthesis Example 11, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0191] Synthesis Example 32 Powder of polyimide resin (A-25) was obtained in the same manner as in Synthesis Example 12, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0192] Synthesis Example 33 Powder of polyimide resin (A-26) was obtained in the same manner as in Synthesis Example 13, except that the acid dianhydride, diamine, and end-capping agent used were replaced as shown in Table 1-2.

[0193] Synthesis Examples 34 to 39 Synthesis of Polyimide Resins (A-27) to (A-32) Powders of polyimide resins (A-27) to (A-32) were obtained in the same manner as in Synthesis Example 5, except that the acid dianhydrides, diamines, and end-capping agents used were replaced as shown in Table 1-2.

[0194] The amic acid ratio, amic acid ester ratio, and imidization ratio of the resulting polyimide resins (A-1) to (A-32) were calculated by the above-mentioned methods, and the results are shown in Tables 1-1 and 1-2.

[0195]

[0196]

[0197] The abbreviations and compound names listed in Tables 1-1 and 1-2 are shown below: ODPA: bis(3,4-dicarboxyphenyl)ether dianhydride BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane DMFDMA: N,N-dimethylformamide dimethyl acetal HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane TPE-R: 1,3-bis(4-aminophenoxy)benzene 4,4'-ODA: 4,4'-diaminodiphenyl ether MAP: 3-aminophenol NA: 5-norbornene-2,3-dicarboxylic anhydride.

[0198] Synthesis Example 41 Synthesis of quinone diazide compound (B-1) Under a dry nitrogen stream, 42.4 g (0.10 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 53.6 g (0.20 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), which is a photoacid generator represented by the following formula:

[0199]

[0200] [Other Components] Thermal crosslinking agent: "Showfree" (registered trademark) PETG (C-1) (aliphatic epoxy thermal crosslinking agent, compound shown in the following chemical formula, manufactured by Resonac Co., Ltd.)

[0201]

[0202] "TEPIC" (registered trademark)-VL (C-2) (an epoxy thermal crosslinking agent containing an isocyanuric ring structure, a compound represented by the following chemical formula, manufactured by Nissan Chemical Industries, Ltd.)

[0203]

[0204] "Epocalic" (registered trademark) DE-102 (C-3) (alicyclic epoxy thermal crosslinking agent, compound shown in the chemical formula below, manufactured by ENEOS Corporation)

[0205]

[0206] "TECHMORE" (registered trademark) VG3101L (C-4) (thermal crosslinking agent having an aromatic ring and an epoxy group, compound represented by the following chemical formula, manufactured by Printec Co., Ltd.)

[0207]

[0208] "NIKALAC" (registered trademark) MX-270 (C-5) (compound represented by the following chemical formula, manufactured by Sanwa Chemical Co., Ltd.)

[0209]

[0210] [Preparation of Resin Compositions] Each component was placed in a 100 mL vial according to the composition shown in Table 2, 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 (V-1 to 46). In Tables 2-1, 2-2, and 2-3, "PGME" represents propylene glycol monomethyl ether, "EL" represents ethyl lactate, "MPA" represents 3-methoxy-N,N-dimethylpropanamide, and "DMPA" represents N,N-dimethylpropionamide.

[0211]

[0212]

[0213]

[0214] Examples 1 to 36, Comparative Examples 1 to 10 The prepared resin compositions were used to evaluate sensitivity, development adhesion, and development residues by the methods described above, and the results are shown in Tables 3-1, 3-2, and 3-3.

[0215]

[0216]

[0217]

[0218] The samples shown in Examples 1 to 36 were judged to have a rating of 3 or more in all of the sensitivity, development adhesion, development residue, and storage stability, and thus had good results.

[0219] On the other hand, the samples shown in Comparative Examples 1 to 10 were inferior in at least one of these properties.

[0220] 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 and interlayer insulating layers of semiconductor elements, on-chip microlenses of solid-state imaging elements, and planarizing layers for various displays and solid-state imaging elements.

[0221] The cured product 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 and interlayer insulating layers of semiconductor elements, on-chip microlenses of solid-state imaging elements, and planarizing layers for various displays and solid-state imaging elements.

Claims

1. A resin composition comprising a polyimide resin (A) having a structure represented by either formula (1) or formula (2) and an amic acid structure, and a photosensitive compound (B), wherein the ratio of the amic acid structure in the polyimide resin (A) is 5% or more and 50% or less. (In formula (1) and formula (2), X １ and X ２ each independently represents a tetravalent organic group containing at least one aromatic ring having 6 to 40 carbon atoms; R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. * represents a bond.

2. X in the above formula (1) and formula (2) １ and X ２ The resin composition according to claim 1 , wherein at least one of the above is a structure represented by formula (3). (In formula (3), R ３ is a direct bond, -SO ２ -, -O-, -S-, -CO-, -C(CF ３ ) ２ - or a hydrocarbon group having 1 to 20 carbon atoms; R ４ and R ５ each independently represents a chlorine atom, a fluorine atom, a cyano group, a nitro group, or a trifluoromethyl group, and a and b each independently represent an integer of 0 to 3. １ is the bond to the nitrogen atom, * ２ indicates the bond to the oxygen atom.) 3. R ​​in the above formula (3) ３ The resin composition according to claim 2, wherein the structure is represented by formula (9) or formula (10). (In formulas (9) and (10), R １９ represents an alkyl group having 1 to 4 carbon atoms, c represents an integer of 1 to 3, d represents 1 or 2, R ２０ and R ２１ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents a bonding point to the aromatic ring. ２０ and R ２１ are not the same structure.) 4. A resin composition according to claim 1 or 2, wherein the polyimide resin (A) has an amic acid ester structure, and the ratio of the amic acid ester structure in the polyimide resin (A) is 20% or more and 90% or less.

5. The resin composition according to claim 1 or 2, further comprising a thermal crosslinking agent (C).

6. The resin composition according to claim 5, wherein the thermal crosslinking agent (C) contains one or more thermal crosslinking agents selected from the group consisting of an isocyanuric ring structure-containing epoxy thermal crosslinking agent, an alicyclic epoxy thermal crosslinking agent, and an aliphatic epoxy thermal crosslinking agent.

7. The resin composition according to claim 1 or 2, further comprising a solvent (D), the solvent (D) being a solvent represented by formula (11) and / or a solvent represented by formula (12), comprising a solvent (D1). (In formulas (11) and (12), a plurality of R ２２ each independently represents an alkyl group having 1 to 6 carbon atoms; R ２３ represents an alkyl group having 2 to 6 carbon atoms.

8. The resin composition according to claim 1 or 2, further comprising a solvent (D), the solvent (D) including a solvent (D2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or higher and 200°C or lower.

9. The resin composition according to claim 7, wherein the solvent (D) contains a solvent (D2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or more and 200°C or less, and the content ratio Y / X, in which the content of the solvent (D1) in the resin composition is X (parts by mass) and the content of the solvent (D2) is Y (parts by mass), is 1 or more and 1,000 or less.

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

11. An organic EL display device comprising the cured product according to claim 10.

12. A semiconductor device comprising the cured product according to claim 10.

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