Photosensitive resin composition, pattern production method, cured product, electronic component, and display device

Abstract

The purpose of the present invention is to provide a photosensitive resin composition that exhibits excellent heat resistance, little film reduction during development, and high sensitivity. The present invention is a photosensitive resin composition containing (a) at least one resin (hereinafter "(a) resin") selected from the group consisting of polyimides, polyamide-imides, polybenzoxazoles, and precursors thereof, (b) an amine compound, and (c) a photoacid generator, wherein the (b) amine compound is a primary amine or a secondary amine, and the (b) amine compound is contained in the amount of 35 parts by mass or more relative to 100 parts by mass of the (a) resin.

Description

Photosensitive resin composition, pattern manufacturing method, cured product, electronic component, and display device

[0001] The present invention relates to a photosensitive resin composition, a method for producing a pattern, a cured product, an electronic component, and a display device.

[0002] Polyimides, polybenzoxazoles, and the like, which have excellent heat resistance, electrical insulation properties, and mechanical properties, are widely used for surface protection films and interlayer insulating films used in electronic components, insulating layers in organic electroluminescent devices, and planarizing films for TFT (thin film transistor) substrates. In recent years, photosensitive resin compositions in which these resins themselves or their precursors are given photosensitivity have come into use. The use of photosensitive resin compositions can simplify the pattern processing process and shorten the complicated manufacturing process.

[0003] Photosensitive resin compositions include positive-type compositions in which the exposed areas become readily soluble in a developer and can be patterned, and negative-type compositions in which the composition itself is readily soluble and the exposed areas become insoluble in a developer.

[0004] Known examples of positive-type photosensitive resin compositions include polyimide, polyamideimide, polybenzoxazole, and precursors thereof to which a quinone diazide compound is added (see, for example, Patent Document 1). Known examples of negative-type photosensitive resin compositions include polyimide, polyamideimide, polybenzoxazole, and precursors thereof to which a photopolymerizable compound and a photopolymerization initiator are added (see, for example, Patent Document 2).

[0005] JP 2011-180473 A JP 2021-120714 A

[0006] In recent years, as semiconductor elements have become increasingly highly integrated and larger, there has been a demand for thinner, smaller, and more uniform film thickness encapsulating resin packages. This has created a need for resins that are more sensitive than ever before, have excellent heat resistance, and are able to reduce the amount of film loss during development.

[0007] However, the technology described in Patent Document 1 has the problem that the difference in dissolution contrast between the unexposed and exposed areas is small, and there is a limit to the reduction in the film thickness reduction during development, and the problem that the heat resistance is reduced due to the quinone diazide compound remaining in the film after development.

[0008] Furthermore, the technique described in Patent Document 2 has a problem in that heat resistance is reduced because a (meth)acrylate is used as a photopolymerization initiator.

[0009] An object of the present invention is to provide a photosensitive resin composition which is excellent in heat resistance, exhibits little film loss during development, and has high sensitivity.

[0010] In order to solve the above-mentioned problems, the photosensitive resin composition of the present invention has the following configurations [1] to

[18] : [1] A photosensitive resin composition containing (a) one or more resins selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, and precursors thereof (hereinafter referred to as "(a) resin"), (b) an amine compound, and (c) a photoacid generator, wherein the (b) amine compound is a primary amine or a secondary amine, and the (b) amine compound is contained in an amount of 35 parts by mass or more per 100 parts by mass of the (a) resin.

[0011] [2] The photosensitive resin composition according to [1], wherein the (a) resin has an acid equivalent of 500 g / mol or more, and the (a) resin has a carboxylic acid equivalent of 500 g / mol or more, or the (a) resin does not have a carboxy group.

[0012] [3] The photosensitive resin composition according to [1] or [2], wherein the (a) resin contains an amide bond in a repeating unit and is a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor.

[0013] [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the resin (a) has an electron-withdrawing group, and the electron-withdrawing group is one or more groups selected from the group consisting of a nitro group, a cyano group, a sulfo group, and a sulfonyl group.

[0014] [5] The photosensitive resin composition according to any one of [1] to [4] above, wherein the (b) amine compound is a monoamine compound.

[0015] [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein the (b) amine compound is a primary amine.

[0016] [7] The photosensitive resin composition according to any one of [1] to [6] above, wherein the (b) amine compound is an aliphatic amine.

[0017] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the pKb of the amine compound (b) is 6 or less.

[0018] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the boiling point of the amine compound (b) under 1 atmosphere is 100°C or higher and 300°C or lower.

[0019]

[10] The photosensitive resin composition according to any one of [1] to [9] above, wherein the resin (a) has an electron-withdrawing group and comprises one or more resins selected from the group consisting of: (a1) a polyimide or polyamideimide containing a structural unit represented by formula (1) (hereinafter referred to as "resin (a1)"); (a2) a polyimide precursor or polyamideimide precursor containing a structural unit represented by formula (2) (hereinafter referred to as "resin (a2)"); (a3) ​​a polyamideimide containing a structural unit represented by formula (3) (hereinafter referred to as "resin (a3)"); (a4) a polybenzoxazole containing a structural unit represented by formula (4) (hereinafter referred to as "resin (a4)"); and (a5) a polybenzoxazole precursor containing a structural unit represented by formula (5) (hereinafter referred to as "resin (a5)"). In formula (1), L １ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. １ is X １ ~X ４ and one of the positions X ５ ~X ８ The linkage is at any one of the positions X ｎ (n=1 to 8) are C-R ｎ (n = 1 to 8). ｎ (n=1 to 8) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. １Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=2 to 3, 6 to 7) has an electron-withdrawing group. * indicates a bonding site. In formula (2), L ２ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. ２ is X １１ ~X １４ and one of the positions X １５ ~X １８ The linkage is at any one of the positions X ｎ (n=11 to 18) are C-R ｎ (n=11 to 18). ｎ (n=9 to 18) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ２ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=12-13, 16-17) has an electron-withdrawing group. * indicates a binding site. In formula (3), L ３ is an amide bond. ３ is X １９ ~X ２２ It is linked to any one of the positions. ｎ (n=19-22) are C-R ｎ (n=19 to 22). ｎ (n=19 to 22) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ｎ At least one of the (n=20 to 21) has an electron-withdrawing group. * indicates a binding site. In formula (4), L ４ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.４ is X ３１ ~X ３５ and one of the positions X ３６ ~X ４０ The linkage is at any one of the positions X ｎ (n=23-40) are C-R ｎ (n=23 to 40). ｎ (n=23 to 40) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ４ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=33, 38) has an electron-withdrawing group. １ is X ２３ ~X ２６ It connects to one of the positions. ２ is X ２７ ~X ３０ It connects to one of the positions. １ and * ２ indicates the binding site. In formula (5), L ５ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. ５ is X ４９ ~X ５３ and one of the positions X ５４ ~X ５８ The linkage is at any one of the positions X ｎ (n=41-58) are C-R ｎ (n = 41 to 58). ｎ (n=41 to 58) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ５ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=51, 56) has an electron-withdrawing group. ３ is X４１ ~X ４４ It connects to one of the positions. ４ is X ４５ ~X ４８ It connects to one of the positions. ３ and * ４ indicates the binding site.

[0020]

[11] When the (a) resin has an (a1) resin, R ｎ (n=1 to 8) any one or more of which has an electron-withdrawing group, and when the (a) resin has an (a2) resin, R ｎ (n=11 to 18) has an electron-withdrawing group, and when the (a) resin has an (a3) ​​resin, R ｎ (n=19 to 22) has an electron-withdrawing group, and when the (a) resin has the (a4) resin, R ｎ (n=23 to 40), any one or more of which has an electron-withdrawing group, and when the (a) resin has an (a5) resin, R ｎ (n=41 to 58), any one or more of which has an electron-withdrawing group.

[0021]

[12] The photosensitive resin composition according to any one of [1] to

[11] above, which satisfies at least one of the following conditions (P1α) and (1α): (P1α) (a) the content of elemental fluorine in the resin structure is 10,000 ppm by mass or less, and (1α) the content of elemental fluorine in the total solid content of the photosensitive resin composition is 1,000 ppm by mass or less.

[0022]

[13] The photosensitive resin composition according to any one of [1] to

[12] above, wherein the (b) amine compound is an amine salt, and the amine salt is a compound containing a cation species having a primary amine structure or a secondary amine structure and an anion species.

[0023]

[14] A method for producing a pattern, comprising: a step of applying the photosensitive resin composition according to any one of the above [1] to

[13] to a substrate; a step of exposing the coated product through a photomask; a step of heating the coated product simultaneously with or after the exposure through the photomask; a step of developing the coated product after heating; and a step of heating the coated product after development.

[0024]

[15] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[13] above.

[0025]

[16] The cured product according to

[15] , wherein the content of the amine compound (b) in the cured product is 0.001% by mass or more and 1.00% by mass or less, relative to 100% by mass of the cured product.

[0026]

[17] An electronic component having the cured product according to

[15] or

[16] above.

[0027]

[18] A display device having the cured product according to

[15] or

[16] .

[0028] The photosensitive resin composition of the present invention reduces the film thickness during development to a small extent and is excellent in sensitivity and heat resistance.

[0029] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be implemented with various modifications depending on the purpose and application.

[0030] A photosensitive resin composition according to an embodiment of the present invention contains (a) one or more resins selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, and precursors thereof (hereinafter referred to as "(a) resin"), (b) an amine compound, and (c) a photoacid generator, wherein the (b) amine compound is a primary amine or a secondary amine, and the (b) amine compound is contained in an amount of 35 parts by mass or more per 100 parts by mass of the (a) resin.

[0031] The photosensitive resin composition according to the embodiment of the present invention contains (c) a photoacid generator, and thus, by irradiating the composition with exposure light corresponding to the contained photoacid generator, an acid can be generated in the composition. In the exposed area, the generated acid acts as a catalyst, and the (a) resin and the (b) amine compound react with each other, thereby lowering the molecular weight of the (a) resin and making it soluble in a developer. Therefore, the photosensitive resin composition according to the embodiment of the present invention exhibits a solubility contrast in a developer between the unexposed area and the exposed area, and the exposed area dissolves, forming a relief pattern.

[0032] <(a) Resin> The photosensitive resin composition according to an embodiment of the present invention contains (a) one or more resins selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, and precursors thereof (hereinafter referred to as "(a) resin"). Among these, the (a) resin is preferably one or more selected from the group consisting of polyimide, polyamideimide, and polyamide because of its high reactivity with the (b) amine compound. Furthermore, from the viewpoint of improving sensitivity, the (a) resin is also preferably polyamide. In the present invention, the (a) resin is more preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor from the viewpoint of improving reactivity with the (b) amine compound and improving sensitivity.

[0033] Polyimides are polymers containing imide bonds in their repeating units. Polyimides can be synthesized by known methods. For example, they can be obtained by dehydrating and cyclizing a reaction product 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, using heat or a catalyst such as an acid or a base. Thus, polyimides contain residues of tetracarboxylic acid and / or its derivatives and residues of diamine and / or its derivatives.

[0034] Polyamideimide is a polymer containing amide and imide bonds in its repeating units. Polyamideimide can be synthesized by known methods. For example, a resin can be obtained by dehydrating and cyclizing a reaction product obtained by reacting trimellitic acid chloride, corresponding trimellitic acid chloride anhydride, or a compound in which some of the hydrogen atoms on the benzene ring are substituted with nitro, amino, or sulfo groups with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, or the like, through heating or a reaction using a catalyst such as an acid or a base.

[0035] Polybenzoxazole is a polymer containing a benzoxazole structure in the repeating unit. Polybenzoxazole can be synthesized by known methods. For example, a resin can be obtained by dehydrating and cyclizing the reaction product obtained by reacting a bisamino-phenol compound with a dicarboxylic acid or the corresponding dicarboxylic acid chloride or dicarboxylic acid activated ester, or the like, through heating or a reaction using a catalyst such as an acid, a base, acetic anhydride, or a carbodiimide compound. Therefore, polybenzoxazole has a dicarboxylic acid residue and a bisamino-phenol residue.

[0036] Polyamide is a polymer containing an amide bond in the repeating unit. Polyamide can be synthesized by a known method. The polyamide is preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor. In the present invention, from the viewpoint of improving the reactivity with the (b) amine compound and improving sensitivity, the (a) resin contains an amide bond in the repeating unit, and is more preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor.

[0037] The polyimide precursor is a polyamide that can be converted to polyimide by heating. By incorporating the polyimide precursor, a resin film with high heat resistance can be obtained. The polyimide precursor can be synthesized by a known method. For example, a resin 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 can be used.

[0038] The polyamide-imide precursor is a polyamide that can be converted to polyamide-imide by heating. By incorporating the polyamide-imide precursor, a resin film with high heat resistance can be obtained. The polyamide-imide precursor can be synthesized by a known method. For example, a resin obtained by reacting trimellitic acid chloride, a corresponding trimellitic acid chloride anhydride, or a compound in which some of the hydrogen atoms on the benzene ring are substituted with a nitro group, an amino group, a sulfo group, or the like with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine can be mentioned.

[0039] The polybenzoxazole precursor is a polyamide that can be converted to polybenzoxazole by heating. By incorporating the polybenzoxazole precursor, a resin film with high heat resistance can be obtained. The polybenzoxazole precursor can be synthesized by a known method. For example, a resin obtained by reacting a bisamino-phenol compound with a dicarboxylic acid, the corresponding dicarboxylic acid chloride, or a dicarboxylic acid activated ester can be used.

[0040] The polyamide may be a resin that does not fall under the category of a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor, such as a resin obtained by reacting a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, or a dicarboxylic acid activated ester.

[0041] Examples of tetracarboxylic acids used in the synthesis of polyimides and polyimide precursors include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic acid, pyromellitic acid, 4,4'-biphenyltetracarboxylic acid, 4,4'-carbonyldiphthalic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenylsulfonetetracarboxylic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, 2,2'-bis(3,4-dicarboxyphenyl)propanoic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 4,4'-(9H-fluorene-9,9-diyl)diphthalic acid, and compounds in which some of the hydrogen atoms on the benzene rings of these compounds have been substituted with nitro groups, amino groups, sulfo groups, or the like.

[0042] Examples of tetracarboxylic dianhydrides used in the synthesis of polyimides and polyimide precursors include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,2'-bis(3,4-dicarboxyphenyl)propanoic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 5,5'-(9H-fluorene-9,9-diyl)bis(2-benzofuran-1,3-dione), and compounds in which some of the hydrogen atoms on the benzene rings are substituted with nitro groups, amino groups, sulfo groups, or the like, but are not limited thereto.

[0043] Examples of the tetracarboxylic acid diester dichlorides used in the synthesis of polyimides and polyimide precursors include, but are not limited to, compounds in which the carboxylic acid of the compounds described above as examples of tetracarboxylic acids is changed to an ester chloride.

[0044] Diamines used in the synthesis of polyimides, polyamideimides, polyimide precursors, and polyamideimide precursors include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diamino-diphenyl ether, 3,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, 4,4'-diamino-diphenyl sulfide, 3,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,4' -diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-biphenyl, 3,4'-diamino-biphenyl, 3,3'-diamino-biphenyl, 4,4'-diamino-benzophenone, 3,4'-diamino-benzophenone, 3,3'-diamino-benzophenone, 4,4'-diamino-diphenylmethane, 3,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 1,4-bis(4-amino-phenoxy)benzene, 1,3-bis(4- 4,4-bis(4-amino-phenoxy)benzene, 1,3-bis(3-amino-phenoxy)benzene, bis[4-(4-amino-phenoxy)phenyl]sulfone, bis[4-(3-amino-phenoxy)phenyl]sulfone, 4,4-bis(4-amino-phenoxy)biphenyl, 4,4-bis(3-amino-phenoxy)biphenyl, bis[4-(4-amino-phenoxy)phenyl]ether, bis[4-(3-amino-phenoxy)phenyl]ether, 1,4-bis(4-amino-phenyl)benzene, 1,3- Bis(4-amino-phenyl)benzene, 9,10-bis(4-amino-phenyl)anthracene, 2,2-bis(4-amino-phenyl)propane, 2,2-bis(4-amino-phenyl)hexafluoropropane, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane, 2,2-bis[4-(4-amino-phenoxy)phenyl]hexafluoropropane, 1,4-bis(3-amino-propyldimethylsilyl)benzene, 3,7-diamino-2,8-dimethyldiphenylene sulfone, 9,Examples of such compounds include, but are not limited to, 9-bis(4-aminophenyl)fluorene and compounds in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc.

[0045] Examples of diisocyanate compounds used in the synthesis of polyimides, polyamideimides, polyimide precursors, and polyamideimide precursors include, but are not limited to, compounds in which the amino groups of the compounds described above as examples of diamines are replaced with isocyanate groups.

[0046] Examples of trimethylsilylated diamines used in the synthesis of polyimides, polyamideimides, polyimide precursors, and polyamideimide precursors include, but are not limited to, compounds in which some of the hydrogen atoms on the benzene ring of the compounds described above as examples of diamines have been substituted with trimethylsilyl groups.

[0047] Examples of bisamino-phenol compounds used in the synthesis of polybenzoxazole and polybenzoxazole precursors include bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-amino-benzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-amino-benzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2'-bis[N-(3-amino-benzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-amino-benzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-amino-benzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-amino-benzoyl)-3-amino-4-hydroxyphenyl]fluorene phenyl]fluorene, N,N'-bis(3-amino-benzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-amino-benzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-amino-benzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-amino-benzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-amino-benzoyl)-3,3'-diamino-4 ,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,2-bis[3-(3-amino-benzamido)-4-hydroxyphenyl]hexafluoropropane and the like.

[0048] Examples of dicarboxylic acids used in the synthesis of polybenzoxazoles and polybenzoxazole precursors include, but are not limited to, terephthalic acid, isophthalic acid, dimer acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

[0049] Examples of dicarboxylic acid chlorides used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, but are not limited to, compounds in which the carboxylic acid of the compounds described above as examples of dicarboxylic acids is changed to a carboxylic acid chloride.

[0050] Examples of dicarboxylic acid active esters used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, but are not limited to, compounds in which the carboxylic acid of the compounds described above as examples of dicarboxylic acids is changed to a carboxylic acid active ester such as a thioester or a phenyl ester.

[0051] When the polyamide is a resin that does not fall under the category of a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor, the diamine, diisocyanate compound, trimethylsilylated diamine, dicarboxylic acid, dicarboxylic acid chloride, and dicarboxylic acid active ester used in the synthesis of such a polyamide include, but are not limited to, the compounds described above.

[0052] The main chain terminals of the (a) resin are preferably capped with a terminal-capping agent such as a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. By capping the main chain terminals with a terminal-capping agent, the storage stability of the photosensitive resin composition can be improved. The proportion of the monoamine used as the terminal-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 60 mol% or less, and particularly preferably 50 mol% or less, based on the total amine components constituting the (a) resin. The proportion of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the terminal-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 100 mol% or less, and particularly preferably 90 mol% or less, based on the diamine components constituting the (a) resin. Multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0053] The weight-average molecular weight of the (a) resin is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, in order to inhibit the dissolution of the unexposed area in a developer and to improve mechanical properties and heat resistance. To improve the solubility of the exposed area in a developer, the weight-average molecular weight is preferably 100,000 or less, more preferably 60,000 or less, and even more preferably 30,000 or less. In the present invention, the weight-average molecular weight is determined by gel permeation chromatography in terms of polystyrene using the method described below.

[0054] From the viewpoint of improving the reactivity with the amine compound (b), the resin (a) preferably has an electron-withdrawing group. In order to further improve the reactivity between the resin (a) and the amine compound (b), the resin (a) more preferably has two or more electron-withdrawing groups. It is even more preferable that the resin (a) has an electron-withdrawing group in a repeating unit.

[0055] In the present invention, the electron-withdrawing group refers to a group having a positive substituent constant σp0 value as defined in Chemistry Handbook, Basic Edition, 5th Revised Edition, II-379 to II-380 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.). Specific examples include a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group, a sulfinyl group, a sulfo group, a halo(cyclo)alkyl group or a haloaryl group, and combinations thereof. The halo(cyclo)alkyl group refers to an at least partially halogenated alkyl group or cycloalkyl group, and the haloaryl group refers to an at least partially halogenated aryl group.

[0056] In order to further improve the reactivity of the (a) resin with the (b) amine compound, the electron-withdrawing group is preferably one or more groups selected from the group consisting of a nitro group, a cyano group, a sulfo group, and a sulfonyl group, and more preferably one or more groups selected from the group consisting of a nitro group, a cyano group, and a sulfo group. The same applies when the (a) resin has an electron-withdrawing group in its repeating unit.

[0057] When the (a) resin contains an amide bond in a repeating unit and is a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor, the (a) resin preferably has an electron-withdrawing group, and the electron-withdrawing group is more preferably one or more groups selected from the group consisting of a nitro group, a cyano group, a sulfo group, and a sulfonyl group.

[0058] The (a) resin preferably has an acidic group in at least one of the main chain, side chain, or end of the resin. The acidic group is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a mercapto group, a carboxy group, a carboxylic anhydride group, or a sulfonic acid group. From the viewpoint of suppressing salt formation of the (b) amine compound by the carboxy group in the (a) resin and suppressing inhibition of the reaction between the (a) resin and the (b) amine compound, it is also preferable that the (a) resin does not have a carboxy group, a carboxylic anhydride group, or a sulfonic acid group.

[0059] In the present invention, from the viewpoint of improving sensitivity, the acid equivalent of the (a) resin is preferably 200 g / mol or more, more preferably 400 g / mol or more. Also in the present invention, from the viewpoints of suppressing film thickness reduction during development, improving reactivity with the (b) amine compound, and improving sensitivity, the acid equivalent of the (a) resin is preferably 500 g / mol or more, more preferably 700 g / mol or more, even more preferably 1,000 g / mol or more, even more preferably 1,500 g / mol or more, and particularly preferably 2,000 g / mol or more. On the other hand, from the viewpoint of suppressing residues after development, the acid equivalent of the (a) resin is preferably 4,000 g / mol or less, more preferably 3,000 g / mol or less, and even more preferably 2,500 g / mol or less.

[0060] In the present invention, from the viewpoint of improving sensitivity, the carboxylic acid equivalent of the (a) resin is preferably 200 g / mol or more, more preferably 400 g / mol or more. Furthermore, from the viewpoints of suppressing film thickness loss during development, improving reactivity with the (b) amine compound, and improving sensitivity, the carboxylic acid equivalent of the (a) resin is preferably 500 g / mol or more, more preferably 700 g / mol or more, even more preferably 1,000 g / mol or more, even more preferably 1,500 g / mol or more, and particularly preferably 2,000 g / mol or more. On the other hand, from the viewpoint of suppressing residues after development, the carboxylic acid equivalent of the (a) resin is preferably 4,000 g / mol or less, more preferably 3,000 g / mol or less, and even more preferably 2,500 g / mol or less. From the viewpoints of suppressing salt formation of the (b) amine compound by carboxy groups in the (a) resin and suppressing reaction inhibition between the (a) resin and the (b) amine compound, it is also preferable that the (a) resin does not have a carboxy group.

[0061] In the present invention, from the viewpoints of suppressing a film thickness reduction during development, (b) improving reactivity with an amine compound, and improving sensitivity, it is more preferable that the (a) resin has an acid equivalent of 500 g / mol or more and a carboxylic acid equivalent of 500 g / mol or more, or that the (a) resin does not have a carboxy group. In such a configuration, the (a) resin contains an amide bond in the repeating unit, and is more preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor.

[0062] The polyimide precursor has two amic acid structures, two amic acid ester structures, two amic acid amide structures, an amic acid structure and an amic acid ester structure, an amic acid structure and an amic acid amide structure, or an amic acid ester structure and an amic acid amide structure in a repeating unit containing an amine residue and a carboxylic acid residue. The amic acid structure refers to a structure having one carboxylic acid amide bond and one carboxy group. The amic acid ester structure refers to a structure having one carboxylic acid amide bond and one carboxylic acid ester bond. The amic acid amide structure refers to a structure having one carboxylic acid amide bond and another carboxylic acid amide bond. The polybenzoxazole precursor has two hydroxyamide structures in a repeating unit containing an amine residue and a carboxylic acid residue. The polyamideimide precursor has an amide structure and an amic acid structure, an amide structure and an amic acid ester structure, or an amide structure and an amic acid amide structure in a repeating unit containing an amine residue and a carboxylic acid residue.

[0063] From the viewpoints of suppressing film thickness loss during development, (b) improving reactivity with an amine compound, and improving sensitivity, the polyimide precursor preferably has a total content of amic acid ester structures (hereinafter referred to as "esterification rate") and amic acid amide structures (hereinafter referred to as "amidation rate") in the total of amic acid structures, amic acid ester structures, amic acid amide structures, and closed-ring imide structures of 40 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more. Meanwhile, the total content of amic acid ester structures and amic acid amide structures is preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less.

[0064] The amic acid ester structure of the polyimide precursor is preferably an ester structure of a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group is not particularly limited, but examples thereof include an aliphatic hydrocarbon group (an alkyl group, an alkenyl group, an alkynyl group, or the like), an alicyclic hydrocarbon group (a cycloalkyl group, a cycloalkylalkyl group, an alkylcycloalkyl group, or the like), an aromatic hydrocarbon group (an aryl group, an arylalkyl group, an alkylaryl group, or the like), a hydroxyalkyl group, an alkoxy group, an alkenyloxy group, an alkoxyalkyl group, an acyl group, or an acylalkyl group.

[0065] The monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl group or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl group or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl group or acylalkyl group having 1 to 20 carbon atoms. From the viewpoints of suppressing film thickness reduction during development, (b) improving reactivity with amine compounds, and improving sensitivity, the alkyl group preferably has 1 or more carbon atoms, more preferably 2 or more, even more preferably 3 or more, and particularly preferably 4 or more. On the other hand, from the viewpoints of suppressing film thickness reduction during development, (b) improving reactivity with amine compounds, and improving sensitivity, the alkyl group preferably has 20 or less carbon atoms, more preferably an alkyl group having 15 or less carbon atoms, and even more preferably an alkyl group having 10 or less carbon atoms.

[0066] The alkyl group is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, 1,2-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, heptyl, octyl, nonyl, and decyl. The alkenyl or alkynyl group is not particularly limited, and examples thereof include groups in which some of the single bonds in the above-mentioned alkyl groups having 2 to 20 carbon atoms have been replaced with unsaturated bonds.

[0067] From the viewpoint of improving the reactivity with the amine compound (b), the (a) resin preferably has an electron-withdrawing group, and the (a) resin preferably contains one or more resins selected from the group consisting of: (a1) a polyimide or polyamideimide containing a structural unit represented by formula (1) (hereinafter referred to as "(a1) resin"), (a2) a polyimide precursor or polyamideimide precursor containing a structural unit represented by formula (2) (hereinafter referred to as "(a2) resin"), (a3) ​​a polyamideimide containing a structural unit represented by formula (3) (hereinafter referred to as "(a3) resin"), (a4) a polybenzoxazole containing a structural unit represented by formula (4) (hereinafter referred to as "(a4) resin"), and (a5) a polybenzoxazole precursor containing a structural unit represented by formula (5) (hereinafter referred to as "(a5) resin").

[0068] It is more preferable that the (a) resin has an electron-withdrawing group in a repeating unit, and that the (a) resin includes one or more resins selected from the group consisting of the (a1) resin, the (a2) resin, the (a3) ​​resin, the (a4) resin, and the (a5) resin.

[0069] From the viewpoint of improving the reactivity between the (a) resin and the (b) amine compound and improving sensitivity, the (a) resin is more preferably the (a2) resin or the (a5) resin.

[0070]

[0071] In formula (1), L １ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.

[0072] The divalent organic group is not particularly limited, and examples thereof include aliphatic hydrocarbon groups (alkylene groups, alkenylene groups, alkynylene groups, etc.), alicyclic hydrocarbon groups (cycloalkylene groups, cycloalkylalkylene groups, alkylcycloalkylene groups, etc.), aromatic hydrocarbon groups (arylene groups, arylalkylene groups, alkylarylene groups, etc.), hydroxyalkylene groups, alkoxyalkylene groups, acylalkylene groups, etc. Among these, cycloalkylene groups, alkylcycloalkylene groups, arylene groups, and alkylarylene groups are more preferred due to their excellent heat resistance, and cycloalkylene groups and arylene groups are particularly preferred.

[0073] The alkylene group is not particularly limited, but examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a 1,2-dimethylethylene group, a pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.

[0074] The cycloalkylene group is not particularly limited, but examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclododecylene group, a cyclohexadecylene group, and a cyclooctadecylene group.

[0075] The arylene group is not particularly limited, but examples thereof include a phenylene group, a naphthylene group, a methylphenylene group, an ethylphenylene group, a methylnaphthylene group, and a dimethylnaphthylene group.

[0076] L １ is X １ ~X ４ and X ５ ~X ８ The linkage occurs at any one of the positions. * indicates the binding site. X ｎ (n=1 to 8) are C-R ｎ (n = 1 to 8). ｎ (n=1 to 8) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms.

[0077] The monovalent organic group is not particularly limited, and examples thereof include aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups, etc.), alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkylalkyl groups, alkylcycloalkyl groups, etc.), aromatic hydrocarbon groups (aryl groups, arylalkyl groups, alkylaryl groups, etc.), hydroxyalkyl groups, alkoxy groups, alkenyloxy groups, alkoxyalkyl groups, acyl groups, acylalkyl groups, etc. Among these, cycloalkyl groups, alkylcycloalkyl groups, aryl groups, and alkylaryl groups are more preferred due to their excellent heat resistance, and cycloalkyl groups and aryl groups are particularly preferred.

[0078] The alkyl group is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1,2-dimethylethyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0079] The cycloalkyl group is not particularly limited, but examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclohexadecyl group, and a cyclooctadecyl group.

[0080] Examples of the alkylcycloalkyl group include a group in which the above alkyl group and a cycloalkyl group are combined.

[0081] The aryl group is not particularly limited, but examples thereof include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.

[0082] The alkylaryl group is not particularly limited, but examples thereof include groups in which the above alkyl group and aryl group are combined.

[0083] L １ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎAt least one of the groups (n=2 to 3, 6 to 7) has an electron-withdrawing group. This is because the action of the electron-withdrawing group increases the reactivity of the imide bond in formula (1) with the amine compound (b). １ is a sulfonyl group or >C(CF ３ ) ２ If so, then L １ Since R has electron-withdrawing properties, ｎ Even if (n=2 to 3, 6 to 7) does not contain an electron-withdrawing group, the reactivity of the imide bond in formula (1) with the amine compound (b) is increased. ｎ (n=2 to 3, 6 to 7) may contain an electron-withdrawing group.

[0084]

[0085] In formula (2), L ２ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. The divalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), L １ Examples of the divalent organic group having 1 to 20 carbon atoms include the organic groups exemplified by L. ２ is X １１ ~X １４ and one of the positions X １５ ~X １８ The * indicates the binding site.

[0086] X ｎ (n=11 to 18) are C-R ｎ (n=11 to 18). ｎ (n=9 to 18) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), R ｎ Examples of the organic groups include the monovalent organic groups having 1 to 20 carbon atoms (n=1 to 8) exemplified above.

[0087] L ２ Even if the sulfonyl group is >C(CF ３ )２ If not, R ｎ At least one of the groups (n=12 to 13, 16 to 17) has an electron-withdrawing group. This is because the action of the electron-withdrawing group increases the reactivity of the amide bond in formula (2) with the amine compound (b). ２ is a sulfonyl group or >C(CF ３ ) ２ If so, then L ２ Since R has electron-withdrawing properties, ｎ Even if (n=12 to 13, 16 to 17) does not contain an electron-withdrawing group, the reactivity of the amide bond in formula (2) with the amine compound (b) is increased. ｎ (n=12 to 13, 16 to 17) may contain an electron-withdrawing group.

[0088]

[0089] In formula (3), L ３ is an amide bond. ３ is X １９ ~X ２２ It is linked to any one of the positions. ｎ (n=19-22) are C-R ｎ (n=19 to 22). ｎ (n=19 to 22) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), R ｎ (n=1 to 8) and the monovalent organic group having 1 to 20 carbon atoms. In order to increase the reactivity of the amide bond in formula (3) with the amine compound (b), R ｎ At least one of the (n=20 to 21) has an electron-withdrawing group. * indicates a binding site.

[0090]

[0091] In formula (4), L ４ represents a single bond, a sulfonyl group, >C(CF ３ ) ２, an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. The divalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), L １ Examples of the divalent organic group having 1 to 20 carbon atoms include the organic groups exemplified by L. ４ is X ３１ ~X ３５ and one of the positions X ３６ ~X ４０ Connect at any one of the positions. １ is X ２３ ~X ２６ It connects to one of the positions. ２ is X ２７ ~X ３０ It connects to one of the positions. １ and * ２ indicates the binding site.

[0092] X ｎ (n=23-40) are C-R ｎ (n=23 to 40). ｎ (n=23 to 40) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), R ｎ Examples of the organic groups include the monovalent organic groups having 1 to 20 carbon atoms (n=1 to 8) exemplified above.

[0093] L ４ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=33, 38) has an electron-withdrawing group. This is because the action of the electron-withdrawing group increases the reactivity of the oxazole ring in formula (4) with the amine compound (b). ４ is a sulfonyl group or >C(CF ３ ) ２ If so, then L ４ Since R has electron-withdrawing properties, ｎEven if (n=33, 38) does not contain an electron-withdrawing group, the reactivity of the oxazole ring in formula (4) with the amine compound (b) is increased. ｎ (n=33, 38) may contain an electron-withdrawing group.

[0094]

[0095] In formula (5), L ５ represents a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. The divalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), L １ Examples of the divalent organic group having 1 to 20 carbon atoms include the organic groups exemplified by L. ５ is X ４９ ~X ５３ and one of the positions X ５４ ~X ５８ Connect at any one of the positions. ３ is X ４１ ~X ４４ It connects to one of the positions. ４ is X ４５ ~X ４８ It connects to one of the positions. ３ and * ４ indicates the binding site.

[0096] X ｎ (n=41-58) are C-R ｎ (n = 41 to 58). ｎ (n=41 to 58) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms is not particularly limited, but for example, in formula (1), R ｎ Examples of the organic groups include the monovalent organic groups having 1 to 20 carbon atoms (n=1 to 8) exemplified above.

[0097] L ５ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎAt least one of the groups (n=51, 56) has an electron-withdrawing group. This is because the action of the electron-withdrawing group increases the reactivity of the amide bond in formula (5) with the amine compound (b). ５ is a sulfonyl group or >C(CF ３ ) ２ If so, then L ５ Since R has electron-withdrawing properties, ｎ Even if (n=51, 56) does not contain an electron-withdrawing group, the reactivity of the amide bond in formula (5) with the amine compound (b) is increased. ｎ (n=51, 56) may contain an electron-withdrawing group.

[0098] In view of improving the reactivity of the (a) resin with the (b) amine compound, when the (a) resin contains the (a1) resin, R ｎ (n=1 to 8) any one or more of which has an electron-withdrawing group, and when the (a) resin has the (a2) resin, R ｎ (n=11 to 18) has an electron-withdrawing group, and when the (a) resin has the (a3) ​​resin, R ｎ (n=19 to 22) has an electron-withdrawing group, and when the (a) resin has the (a4) resin, R ｎ (n=23 to 40) has an electron-withdrawing group, and when the (a) resin has the (a5) resin, R ｎ It is preferable that at least one of (n=41 to 58) has an electron-withdrawing group.

[0099] <Content of Fluorine Element in the Structure of (a) Resin> From the viewpoints of suppressing film thickness reduction during development and (b) improving reactivity with amine compounds and improving sensitivity, it is preferable that the (a) resin satisfy the following condition (P1α). It is more preferable that the (a) resin further satisfy the following condition (P2α). (P1α) The content of fluorine element in the structure of the (a) resin is 10,000 ppm by mass or less. (P2α) The content of fluoride ions in the structure of the (a) resin is 10,000 ppm by mass or less.

[0100] From the viewpoint of the effects of the present invention, the content of elemental fluorine in the structure of (a) resin is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of the effects of the present invention, the content of elemental fluorine is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, even more preferably 500 ppm by mass or less, particularly preferably 300 ppm by mass or less, and most preferably 100 ppm by mass or less. Furthermore, the fluorine content is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.

[0101] The preferred range of the content of fluoride ions in the structure of the (a) resin is the same as the preferred range of the content of fluorine element in the structure of the (a) resin.

[0102] The content of elemental fluorine in the structure of the (a) resin may be 0 ppm by mass, and the content of fluoride ions in the structure of the (a) resin may also be 0 ppm by mass.

[0103] By incorporating an (a) resin having a fluorine content of a specific value or less into a photosensitive resin composition, the content of fluorine elements, fluoride ions, or anions containing fluorine elements derived from these resins is reduced to a specific value or less. It is therefore believed that protons in the photosensitive resin composition are locally activated due to interactions such as hydrogen bonding between the components in the photosensitive resin composition. Therefore, the localized solubility promotion effect in the developer is thought to suppress the film thickness loss during development while significantly improving sensitivity. Furthermore, the suppression of steric hindrance derived from fluorine elements and fluoride ions is thought to promote the reaction between the (a) resin and the (b) amine compound, resulting in a significant improvement in sensitivity.

[0104] From the viewpoints of suppressing film thickness reduction during development and (b) improving reactivity with an amine compound and improving sensitivity, the photosensitive resin composition of the present invention preferably satisfies at least one of the above condition (P1α) and the following condition (1α). The photosensitive resin composition of the present invention more preferably further satisfies at least one of the above condition (P2α) and the following condition (2α): (1α) the content of elemental fluorine in the total solid content of the photosensitive resin composition is 1,000 ppm by mass or less; and (2α) the content of fluoride ions in the total solid content of the photosensitive resin composition is 1,000 ppm by mass or less.

[0105] From the viewpoint of the effects of the present invention, the content of elemental fluorine in the total solid content of the photosensitive resin composition is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of the effects of the present invention, the content of elemental fluorine is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 300 ppm by mass or less, and particularly preferably 100 ppm by mass or less. Furthermore, the content of elemental fluorine is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.

[0106] The preferred range of the content of fluoride ions in the total solid content of the photosensitive resin composition is the same as the preferred range of the content of elemental fluorine in the total solid content of the photosensitive resin composition described above.

[0107] The content of elemental fluorine in the total solid content of the photosensitive resin composition may be 0 ppm by mass. The content of fluoride ions in the total solid content of the photosensitive resin composition may also be 0 ppm by mass. When the content of elemental fluorine and / or the content of fluoride ions in the total solid content of the photosensitive resin composition exceeds 0 ppm by mass, the photosensitive resin composition of the present invention preferably contains (a) resin, (b) amine compound, or (c) photoacid generator having a fluorine atom or a fluoride ion in its structure, or further contains a component containing elemental fluorine and / or a component containing fluoride ions.

[0108] By controlling the content of compounds containing fluorine atoms in their structures or components containing fluorine atoms in the photosensitive resin composition to a specific value or less, the content of fluorine atoms, fluoride ions, or anions containing fluorine atoms derived from these components is controlled to a specific value or less. As a result, it is believed that protons in the photosensitive resin composition are locally activated due to interactions such as hydrogen bonding between the components in the photosensitive resin composition. Therefore, it is believed that the local dissolution promotion effect in the developer suppresses the amount of film thickness loss during development while significantly improving sensitivity. Furthermore, it is believed that the suppression of steric hindrance derived from fluorine atoms and fluoride ions promotes the reaction between (a) resin and (b) amine compound, thereby significantly improving sensitivity.

[0109] In order to further improve the heat resistance of the cured product obtained by curing the photosensitive resin composition, the content of the (a) resin is preferably 3% by mass or more relative to 100% by mass of the photosensitive resin composition. In addition, in order to obtain a photosensitive resin composition with higher sensitivity, the content of the (a) resin is preferably 30% by mass or less relative to 100% by mass of the photosensitive resin composition.

[0110] <(b) Amine Compound> The photosensitive resin composition according to an embodiment of the present invention contains an amine compound (b). The amine compound (b) is a primary amine or a secondary amine. The amine compound (b) preferably includes one or more compounds selected from the group consisting of monoamine compounds, diamine compounds, triamine compounds, and tetramine compounds. From the viewpoint of suppressing residues after development, the amine compound (b) is more preferably a monoamine compound. From the viewpoint of improving sensitivity, the amine compound (b) preferably includes one or more compounds selected from the group consisting of diamine compounds, triamine compounds, and tetramine compounds. The amine compound (b) may be a polyamine compound having five or more amino groups in the molecule. The number of amino groups in the polyamine compound is preferably seven or more, more preferably ten or more. Preferably, it is 100 or less, more preferably 50 or less, and even more preferably 20 or less.

[0111] The photosensitive resin composition of the present invention preferably contains a monoamine compound which is a primary amine or a secondary amine. Examples of the monoamine compound include R ５９ NH ２ a compound represented by R ６０ ２ Examples of the aromatic hydrocarbon include compounds represented by NH, cyclic compounds such as pyrrolidine, piperidine, indole, and pyrrole, and heteroaromatic compounds.

[0112] Here, R ５９ and R ６０ are each independently a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group (an alkyl group, an alkenyl group, an alkynyl group, etc.), an alicyclic hydrocarbon group (a cycloalkyl group, a cycloalkylalkyl group, an alkylcycloalkyl group, etc.), an aromatic hydrocarbon group (an aryl group, an arylalkyl group, an alkylaryl group, etc.), a hydroxyalkyl group, an alkoxy group, an alkenyloxy group, an alkoxyalkyl group, an acyl group, and an acylalkyl group.

[0113] The monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl group or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl group or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl group or acylalkyl group having 1 to 20 carbon atoms. Among these, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkylalkyl group, an arylalkyl group, a hydroxyalkyl group, an alkoxy group, an alkenyloxy group, an alkoxyalkyl group, an acyl group, or an acylalkyl group is more preferred, and an alkyl group is particularly preferred, because of the small steric hindrance and improved reactivity with the (a) resin.

[0114] The alkyl group is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, 1,2-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, heptyl, octyl, nonyl, and decyl. The alkenyl or alkynyl group is not particularly limited, and examples thereof include groups in which some of the single bonds in the above-mentioned alkyl groups having 2 to 20 carbon atoms have been replaced with unsaturated bonds.

[0115] The cycloalkyl group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclohexadecyl group, and a cyclooctadecyl group. Examples of the cycloalkylalkyl group include a group formed by combining the above-mentioned cycloalkyl group with an alkyl group.

[0116] The aryl group or alkylaryl group is not particularly limited, but examples thereof include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group. The arylalkyl group is not particularly limited, but examples thereof include a group formed by combining the above-mentioned aryl group with an alkyl group.

[0117] The hydroxyalkyl group is not particularly limited, but examples thereof include groups in which some of the hydrogen atoms of the above-mentioned alkyl groups having 1 to 20 carbon atoms have been replaced with hydroxy groups. The alkoxy group or alkenyloxy group is not particularly limited, but examples thereof include groups in which an oxygen atom is bonded to the above-mentioned alkyl group having 1 to 20 carbon atoms or alkenyl group having 2 to 20 carbon atoms. The alkoxyalkyl group is not particularly limited, but examples thereof include groups in which some of the single bonds of the above-mentioned alkyl group having 1 to 20 carbon atoms have been replaced with ether bonds.

[0118] The acyl group or acylalkyl group is not particularly limited, but examples include groups in which some of the two hydrogen atoms on the same carbon atom of the above-mentioned alkyl group having 1 to 20 carbon atoms are replaced with double bonds to oxygen atoms.

[0119] In the cyclic compounds or heteroaromatic compounds, some of the hydrogen atoms on the carbon atoms may be substituted with a hydroxy group, a carboxy group, an aldehyde group, a sulfo group, etc. In the cyclic compounds or heteroaromatic compounds, the molecule has -CH ２ When - is present, -CH ２ A part of the - may be substituted with an ether bond, an ester bond, a carbonyl group, a sulfonyl group, or the like.

[0120] The (b) amine compound is a primary or secondary amine, which reduces steric hindrance and enhances reactivity with the (a) resin. To enhance this effect, the (b) amine compound is preferably a primary amine. To further enhance reactivity with the (a) resin, the (b) amine compound is preferably an aliphatic amine, alicyclic amine, or cyclic amine, in which electron pairs are easily localized on the nitrogen atom of the amine, and more preferably an aliphatic amine. The term "aliphatic amine" refers to a compound in which the above-described aliphatic hydrocarbon group is bonded to the nitrogen atom of the amino group. The term "alicyclic amine" refers to a compound in which the above-described alicyclic hydrocarbon group is bonded to the nitrogen atom of the amino group. The term "cyclic amine" refers to a compound in which the nitrogen atom of the amino group is a ring member atom of a non-heteroaromatic cyclic structure. The (b) amine compound is also preferably an aromatic amine or a heteroaromatic amine from the viewpoints of controlling reactivity with the (a) resin and improving the storage stability of the photosensitive resin composition. The term "aromatic amine" refers to a compound in which the above-described aromatic hydrocarbon group is bonded to the nitrogen atom of the amino group. Heteroaromatic amines refer to compounds in which the nitrogen atom of the amino group is a member atom of a heteroaromatic ring.

[0121] Since the reactivity of the (b) amine compound with the (a) resin improves as the basicity increases, the base dissociation constant (pKb) thereof is preferably 6 or less, and more preferably 4 or less. There is no particular lower limit for the pKb of the (b) amine compound, but it is preferably −14 or more.

[0122] Specific examples of preferred (b) amine compounds are not particularly limited, but include primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, 1,2-dimethylethylamine, pentylamine, 1-methylbutylamine, 2-methylbutylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, amino-methanol, amino-ethanol, 3-amino-1-methyl-2-methyl ...1-methyl-2-methyl-1-methyl-1-methyl-2-methyl-1-methyl-1-methyl-2-methyl-1-methyl-1-methyl-2-methyl-1-methyl-1-methyl-2-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl -propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 9-amino-1-nonanol, 10-amino-1-decanol, 11-amino-1-undecanol, 12-amino-1-dodecanol, 13-amino-1-tridecanol, 14-amino-1-tetradecanol, 15-amino-1-pentadecanol, 16-amino-1-hexadecanol, 17-amino-1-heptadecanol, 18-amino-1-octadecanol, benzylamine, aniline, and the like.

[0123] The aliphatic amine is not particularly limited, but examples thereof include methylamine, ethylamine, propylamine, isopropylamine, butylamine, 1,2-dimethylethylamine, pentylamine, 1-methylbutylamine, 2-methylbutylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, amino-methanol, amino-ethanol, and 3-amino-1-propanoic acid. Examples of amino-1-isopropyl alcohol include 1-amino-1-pentanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 9-amino-1-nonanol, 10-amino-1-decanol, 11-amino-1-undecanol, 12-amino-1-dodecanol, 13-amino-1-tridecanol, 14-amino-1-tetradecanol, 15-amino-1-pentadecanol, 16-amino-1-hexadecanol, 17-amino-1-heptadecanol, and 18-amino-1-octadecanol.

[0124] The monoamine compound having a pKb of 6 or less is not particularly limited, but examples thereof include methylamine, ethylamine, propylamine, isopropylamine, butylamine, 1,2-dimethylethylamine, pentylamine, 1-methylbutylamine, 2-methylbutylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, amino-methanol, amino-ethanol, 3-amino- Examples of the amino-1-propanol include 1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 9-amino-1-nonanol, 10-amino-1-decanol, 11-amino-1-undecanol, 12-amino-1-dodecanol, 13-amino-1-tridecanol, 14-amino-1-tetradecanol, 15-amino-1-pentadecanol, 16-amino-1-hexadecanol, 17-amino-1-heptadecanol, and 18-amino-1-octadecanol.

[0125] The (b) amine compound is preferably removable by heating during or after the reaction with the (a) resin, not only from the viewpoint of improving the heat resistance of the cured product obtained by curing the photosensitive resin composition, but also to reduce the amount of the (b) amine compound remaining in the unexposed areas and thereby reduce the amount of film loss during development. Furthermore, it is preferably removable at a moderate temperature to prevent deterioration of the cured product due to heating at high temperatures. From these viewpoints, the boiling point of the (b) amine compound at 1 atmosphere is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. Meanwhile, in order to allow the (b) amine compound to remain in the photosensitive resin composition until the step of reacting with the (a) resin, the boiling point of the (b) amine compound at 1 atmosphere is preferably 100°C or higher, more preferably 130°C or higher.

[0126] The (b) amine compound is preferably an amine salt from the viewpoints of controlling the reactivity with the (a) resin and improving the storage stability of the photosensitive resin composition. Furthermore, the amine salt is preferably a compound containing a cation species having a primary amine structure or a secondary amine structure and an anion species from the viewpoints of improving the reactivity with the (a) resin and the (b) amine compound and improving the sensitivity.

[0127] The cationic species in the amine salt preferably contains a structure derived from one or more compounds selected from the group consisting of the monoamine compounds, diamine compounds, triamine compounds, and tetramine compounds. The cationic species in the amine salt also preferably contains a structure derived from the polyamine compounds having five or more amino groups in the molecule. The cationic species in the amine salt is preferably composed of the amine compounds described above. Examples and preferred descriptions of the amine compounds are the same as those described above.

[0128] The anion species in the amine salt is preferably one or more selected from the group consisting of sulfonate ion, formate ion, acetate ion, oxalate ion, phenoxy ion, sulfate ion, sulfite ion, nitrate ion, nitrite ion, phosphate ion, phosphite ion, hypophosphite ion, fluoride ion, chloride ion, bromide ion, and iodide ion.

[0129] The sulfonate ion preferably has a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group is not particularly limited, but examples thereof include an aliphatic hydrocarbon group (an alkyl group, an alkenyl group, an alkynyl group, or the like), an alicyclic hydrocarbon group (a cycloalkyl group, a cycloalkylalkyl group, an alkylcycloalkyl group, or the like), an aromatic hydrocarbon group (an aryl group, an arylalkyl group, an alkylaryl group, or the like), a hydroxyalkyl group, an alkoxy group, an alkenyloxy group, an alkoxyalkyl group, an acyl group, or an acylalkyl group.

[0130] The monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl group or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl group or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl group or acylalkyl group having 1 to 20 carbon atoms.

[0131] In the present invention, in order to obtain a highly sensitive photosensitive resin composition, the content of the (b) amine compound is 35 parts by mass or more per 100 parts by mass of the (a) resin in the photosensitive resin composition. In the present invention, the content of the monoamine compound is preferably 35 parts by mass or more per 100 parts by mass of the (a) resin in the photosensitive resin composition. In the present invention, the content of the (b) amine compound is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, per 100 parts by mass of the (a) resin. On the other hand, in order to reduce the amount of the (b) amine compound remaining in the unexposed areas and thereby suppress the film thickness loss during development, and to reduce the amount of the (b) amine compound remaining in the cured film and thereby improve heat resistance, the content of the (b) amine compound is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less, per 100 parts by mass of the (a) resin in the photosensitive resin composition.

[0132] <(c) Photoacid Generator> The photosensitive resin composition according to an embodiment of the present invention contains (c) a photoacid generator. A photoacid generator is a compound that has the function of generating an acid upon exposure to light. Any known photoacid generator (c) can be used as long as it does not impair the effects of the present invention.

[0133] (c) Examples of photoacid generators include onium salt-type ionic photoacid generators and nonionic photoacid generators. An onium salt refers to a compound formed when a compound having an electron pair not involved in a chemical bond forms a coordinate bond with another cationic compound via that electron pair. In the ionic photoacid generator, the cationic portion of the onium salt determines the photochemical properties (molar absorption coefficient, absorption wavelength, quantum yield), while the anionic portion determines the strength of the acid generated. On the other hand, nonionic photoacid generators are photoacid generators in which the light-absorbing portion and the acid are connected via an ester bond.

[0134] The ionic compound is preferably one that does not contain heavy metals or halogen ions, and more preferably a triorganosulfonium salt compound. Specific examples of the triorganosulfonium salt compound include triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate ("SP-056", trade name, manufactured by ADEKA Corporation); the above-mentioned sulfonates of dimethyl-1-naphthylsulfonium; the above-mentioned sulfonates of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the above-mentioned sulfonates of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the above-mentioned sulfonates of diphenyliodonium.

[0135] As the nonionic photoacid generator, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, a sulfonimide compound, a phosphate compound, a sulfonebenzotriazole compound, or the like can be used.

[0136] Specific examples of diazomethane compounds include bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0137] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred examples of the sulfone compound include 2-(p-toluenesulfonyl)acetophenone, bis(phenylsulfonyl)methane, etc.

[0138] Specific examples of the sulfonate ester compound include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, iminosulfonate ester compounds, etc. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, 2,6-(dinitrobenzyl)phenyl sulfonate, etc.

[0139] Specific examples of carboxylic acid ester compounds include carboxylic acid 2-nitrobenzyl ester.

[0140] (c) The photoacid generator preferably contains a nonionic photoacid generator. By including a nonionic photoacid generator in (c), the photosensitive resin composition can have higher sensitivity.

[0141] It is more preferable that the (c) photoacid generator contains a photoacid generator in which the acid dissociation constant (pKa) of the acidic group generated by light is in the range of −14 to 2. This allows the acidic group generated by light to efficiently act as an acid in the reaction between the (a) resin and the (b) amine compound.

[0142] Specific examples of photoacid generators in which the acid dissociation constant (pKa) of the acidic group generated by light is in the range of −14 to 2 include photoacid generators in which the acid generated by light is trifluoromethanesulfonic acid (pKa=−14), nonafluorobutanesulfonic acid (pKa=−3.57), p-toluenesulfonic acid (pKa=−2.8), methanesulfonic acid (pKa=−2.6), etc.

[0143] It is more preferable that the (c) photoacid generator contains an oxime sulfonate compound and / or an imide sulfonate compound. The oxime sulfonate compound and the imide sulfonate compound are nonionic photoacid generators, and the acidic group generated by light is a sulfo group, so that the pKa is high and the photosensitive resin composition can have higher sensitivity.

[0144] The oxime sulfonate compound can be represented by the following structure:

[0145]

[0146] R ６１ is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a trifluoromethanesulfonic acid group, a nonafluorobutyl group, a perfluorooctyl group, a (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl group, a benzyl group, a phenyl group, a tosyl group, and a naphthyl group.

[0147] R ６２ and R ６３ is a monovalent organic group having 1 to 30 carbon atoms. ６３ and R ６４ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include a cyano group, a trifluoromethyl group, a hexafluoropropyl group, a pentafluorobutyl group, a dodecafluorohexyl group, a phenyl group, a 4-methoxyphenyl group, a 2-fluorenyl group, and a 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl group.

[0148] R ６４ is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the monovalent organic group having 3 to 30 carbon atoms include the following structures.

[0149] * indicates the binding site.

[0150] Specific examples of oxime sulfonates include "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (benzeneacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (benzeneacetonitrile, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylidene), and PAG-203 (all manufactured by BASF Japan Ltd.), and PAI-101 ((Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Co., Ltd.).

[0151] The imidosulfonate compound can be represented by the following structure:

[0152]

[0153] R ６５ is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include R ６１ Examples of the groups include those given as specific examples of the above.

[0154] R ６６ and R ６７ is a monovalent organic group having 1 to 30 carbon atoms. ６６ and R ６７ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include R ６２ and R ６３ Examples of the groups include those given as specific examples of the above.

[0155] R ６８ is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of divalent organic groups having 3 to 30 carbon atoms include the following structures:

[0156]

[0157] R ６９is a monovalent organic group having 1 to 12 carbon atoms. t is an integer of 0 to 2. Specific examples of monovalent organic groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecanyl group, a 1-(hex-1-en-1-yl) group, and a 1-(4-butoxyphenethyl) group. * indicates a bonding site.

[0158] Examples of the imide sulfonate compound include N-hydroxynaphthalimide triflate, "ADEKA ARCLES" (registered trademark), SP-606 (4-butyl-N-hydroxy-naphthalimide triflate, manufactured by ADEKA Corporation), NA-101 (N-hydroxynaphthalimide-p-toluenesulfonate), and NA-106 (N-hydroxynaphthalimide camphorsulfonate, all manufactured by Midori Chemical Industry Co., Ltd.).

[0159] In the present invention, in order to obtain a photosensitive resin composition with higher sensitivity, the content of the (c) photoacid generator 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, per 100 parts by mass of the (a) resin in the photosensitive resin composition. On the other hand, in order to reduce the amount of the (c) photoacid generator remaining in the cured film and further improve heat resistance, the content of the (c) photoacid generator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the (a) resin in the photosensitive resin composition.

[0160] The photosensitive resin composition according to the embodiment of the present invention preferably further contains a solvent. By incorporating a solvent, a film of the composition can be formed on a substrate with a desired thickness, and the effect of improving the thickness uniformity of the coating film is significantly enhanced. From the viewpoint of solubility of various resins and various additives, the solvent preferably contains a solvent having a carbonyl group, a solvent having an ester bond, a solvent having at least three ether bonds, or a solvent having an alcoholic hydroxyl group. From the viewpoint of improving the thickness uniformity of the coating film, the solvent is preferably a compound having a boiling point of 110°C or higher at atmospheric pressure. On the other hand, from the viewpoint of improving flatness by suppressing film shrinkage during thermal curing, a compound having a boiling point of 250°C or lower at atmospheric pressure is preferred. The content ratio of the solvent in the photosensitive composition of the present invention can be appropriately adjusted depending on the coating method, etc. For example, when forming a coating film by spin coating, the solvent typically accounts for 50 to 95% by mass of the entire photosensitive composition.

[0161] The carbonyl group is preferably an alkylcarbonyl group, a dialkylcarbonyl group, or a formyl group. The ester bond is preferably a carboxylic acid ester bond, a carbonate ester bond, or a formate ester bond. Among the carboxylic acid ester bonds, an acetate bond, a propionate bond, or a butyrate bond is more preferred. The carbonyl group is more preferably a cyclic carbonyl group. The carboxylic acid ester bond is more preferably a cyclic carboxylic acid ester bond. The carbonate ester bond is more preferably a cyclic carbonate ester bond.

[0162] Examples of solvents having a carbonyl group include 2-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0163] The use of a solvent having a carbonyl group, a solvent having an ester bond, a solvent having at least three ether bonds, or a solvent having an alcoholic hydroxyl group is preferred from the viewpoint of suppressing the reaction inhibition of the acid generated from the photoacid generator (c).Furthermore, from the viewpoint of suppressing the reaction inhibition of the acid generated from the photoacid generator (c), the solvent having a carbonyl group, a solvent having an ester bond, a solvent having at least three ether bonds, and a solvent having an alcoholic hydroxyl group preferably does not have an amide group, an imide group, a urea bond, or a urethane bond.

[0164] Examples of solvents having an ester bond include 3-methoxy-n-butyl acetate, 3-methyl-3-methoxy-n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, diethylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, 1,4-butanediol diacetate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, δ-caprolactone, and ε-butyrolactone.

[0165] In the photosensitive composition of the present invention, from the viewpoints of suppressing reaction inhibition of the acid generated from (c) the photoacid generator and improving sensitivity, the total content of the solvent having a carbonyl group, the solvent having an ester bond, the solvent having at least three ether bonds, and the solvent having an alcoholic hydroxyl group in the solvent is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, still more preferably 70 to 100 mass%, and particularly preferably 90 to 100 mass%.

[0166] In the photosensitive composition of the present invention, from the viewpoints of suppressing reaction inhibition of the acid generated from the (c) photoacid generator and improving sensitivity, the total content of the solvent having a carbonyl group and the solvent having an ester bond in the solvent is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, still more preferably 70 to 100 mass%, and particularly preferably 90 to 100 mass%.

[0167] The photosensitive resin composition according to the embodiment of the present invention may contain other additives in addition to those described above, such as a dissolution promoter, a sensitizer, a silane coupling agent, and a surfactant.

[0168] <Cured Product> The cured product according to the embodiment of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. Curing conditions include heat treatment at 150°C to 350°C. This heat treatment promotes a thermal crosslinking reaction, improving heat resistance and chemical resistance. Preferred conditions for the heat treatment will be described later.

[0169] To further improve the heat resistance of the cured product, the content of the (b) amine compound in the cured product is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.010% by mass or more, relative to 100% by mass of the cured product, while the content of the (b) amine compound in the cured product is preferably 1.00% by mass or less, more preferably 0.50% by mass or less, and even more preferably 0.30% by mass or less, relative to 100% by mass of the cured product.

[0170] <Pattern Manufacturing Method> A pattern manufacturing method using the photosensitive resin composition according to an embodiment of the present invention includes the steps of: applying the photosensitive resin composition of the present invention to a substrate (hereinafter, "step (a-1)"); exposing the coated product through a photomask (hereinafter, "step (b-1)"); heating the coated product simultaneously with or after exposure through the photomask (hereinafter, "step (b-2)"); developing the heated coated product (hereinafter, "step (c-1)"); and heating the developed coated product (hereinafter, "step (d-1)"). Step (a-1) is a step of applying the photosensitive resin composition to a substrate. The substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafers, ceramic deposition substrates, metal-plated substrates, sapphire, and gallium arsenide.

[0171] The photosensitive resin composition can be applied to a substrate by any known method, including, for example, a full-surface coating apparatus such as spin coating, dip coating, curtain flow coating, spray coating, or slit coating, or a printing apparatus such as screen printing, roll coating, microgravure coating, or inkjet printing.

[0172] After coating the photosensitive resin composition on the substrate, it may be dried to remove the solvent, etc. Drying is performed using a vacuum drying device or a heating device such as a hot plate or oven. When using a heating device, drying is preferably performed at a temperature range of 50°C or higher and 150°C or lower for 30 seconds to 30 minutes. The film thickness of the coating (after drying, if drying is performed after coating) is preferably 0.1 μm or higher and 100 μm or lower.

[0173] The above step (b-1) is a step of exposing the coated product to light through a photomask. The coated product is exposed to light through a mask having a desired pattern. The wavelength of the electromagnetic waves irradiated in the above step (b-1) is not particularly limited, and examples thereof include electromagnetic waves having a wavelength of 300 to 450 nm, such as g-line (436 nm), h-line (405 nm), or i-line (365 nm). Of these, it is preferable to irradiate electromagnetic waves having a wavelength of 365 nm.

[0174] Examples of light sources used in exposure include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and metal halide lamps. If necessary, the wavelength of the irradiated light may be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

[0175] The above-mentioned step (b-2) is a step of heating the coated material simultaneously with or after exposure through a photomask. The acid generated from the (c) photoacid generator in the exposed area acts as a catalyst, and heating promotes the reaction between the (a) resin and the (b) amine compound, thereby expanding the solubility contrast in the developer between the unexposed and exposed areas. Heating can be performed using an oven, hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like. The heating temperature is preferably 80°C or higher to enhance the reactivity between the (a) resin and the (b) amine compound. It is more preferably 100°C or higher, and even more preferably 130°C or higher. From the viewpoint of preventing thermal crosslinking of the (a) resin and expanding the solubility contrast in the developer between the unexposed and exposed areas, it is preferably 250°C or lower. It is more preferably 200°C, and even more preferably 180°C or lower. The heating time is preferably 10 seconds to 1 hour, and more preferably 30 seconds to 30 minutes.

[0176] The above-mentioned step (c-1) is a step of developing the coated product after heating. To form a pattern of the photosensitive resin composition, the exposed area is removed using a developer after exposure. The developer used for development is not particularly limited, but an organic solvent or an alkaline aqueous solution can be used. The organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone (GBL), dimethylacrylamide, and α-acetyl-γ-butyrolactone; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone (CP), cyclohexanone, isobutyl ketone, and methyl isobutyl ketone can be used alone or in combination.

[0177] The alkaline aqueous solution is typically an alkaline aqueous solution in which an alkaline compound is dissolved. Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate. In some cases, polar solvents such as N-methyl-2-pyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone (GBL), dimethylacrylamide, and α-acetyl-γ-butyrolactone, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone (CP), cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination to the alkaline aqueous solution.

[0178] After development, it is preferable to perform a rinse treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, examples of the solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may also be added to the water for rinsing treatment.

[0179] The above-mentioned step (d-1) is a step of heating the coating after development. After development, a temperature of 150°C to 350°C is applied to promote a thermal crosslinking reaction, thereby improving heat resistance and chemical resistance. This heat treatment may be carried out, for example, by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. One example is heat treatment at 130°C and 200°C for 30 minutes each.

[0180] In the present invention, the lower limit of the heating temperature is preferably 200° C. or higher, more preferably 250° C. or higher, and even more preferably 300° C. or higher in order to increase the progress of the thermal crosslinking reaction and remove the (b) amine compound. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 300° C. or lower in order to prevent deterioration of the cured product.

[0181] The heating atmosphere is not particularly limited, but may be air or an inert atmosphere such as nitrogen or argon gas, etc. To prevent deterioration, it is preferable to perform the heating in an inert atmosphere.

[0182] The cured product obtained by the pattern manufacturing method according to the embodiment of the present invention is a cured product mainly composed of polyimide, polyamideimide, or polybenzoxazole, and therefore has excellent heat resistance.

[0183] <Electronic Components> A cured product obtained by curing the photosensitive resin composition according to an embodiment of the present invention can be used as an insulating film or a protective film constituting an electronic component. Examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, and passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.

[0184] <Organic EL Display Device> A cured product obtained by curing the photosensitive resin composition according to an embodiment of the present invention can be used as an insulating film or a protective film constituting a display device. The cured product of the photosensitive resin composition of the present invention is particularly suitable for use as a planarizing layer or an insulating layer constituting an organic EL display device. Specifically, an organic EL display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, in which the planarizing layer and / or the insulating layer comprises the cured film, is preferred. Taking an active matrix display device as an example, a substrate such as glass or a resin film has TFTs and wiring located on the sides of the TFTs and connected to the TFTs, a planarizing layer on top of the TFTs to cover the irregularities, and a display element on the planarizing layer. The display element and the wiring are connected via contact holes formed in the planarizing layer.

[0185] The cured product obtained by curing the photosensitive resin composition according to the embodiment of the present invention is excellent in planarization properties and pattern dimensional stability, and is therefore preferably provided as a planarization layer in an organic EL display device. In particular, in recent years, flexible organic EL display devices have become mainstream, and the organic EL display device may have a substrate having the above-mentioned drive circuit formed of a resin film.

[0186] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The names of the compounds used, for which abbreviations are used, are shown below.

[0187] <Carboxylic acid derivatives> BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride NBPDA: 6-nitro-3,3',4,4'-biphenyltetracarboxylic dianhydride DSDA: 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride BP-HBT: A mixture of dicarboxylic acid derivatives obtained by reacting 4,4'-biphenyldicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole BPDCC: 4,4'-biphenyldicarboxylic acid dichloride TMAC: Trimellitic anhydride chloride <Amine derivatives> DABP: 4,4'-diamino-biphenyl DADHBP: 3,3'-diamino-4,4'-dihydroxybiphenyl

[0188] <Esterifying agent> DFA: N,N-dimethylformamide dimethyl acetal <(b) Amine compound> HA: hexylamine (primary aliphatic amine, boiling point 133°C, pKb 3.4) DBA: dibutylamine (secondary aliphatic amine, boiling point 159°C, pKb 2.7) TBA: tributylamine (tertiary aliphatic amine, boiling point 216°C, pKb 4.0) BEA: benzylamine (primary aromatic amine, boiling point 185°C, pKb 4.7) AN: aniline (primary aromatic amine, boiling point 184°C, pKb 9.4) BA: butylamine (primary aliphatic amine, boiling point 78°C, pKb 3.2) PA: pentylamine (primary aliphatic amine, boiling point 104°C, pKb 3.8) OA: Octylamine (primary aliphatic amine, boiling point 176°C, pKb 3.3) AH: 6-amino-1-hexanol (primary aliphatic amine, boiling point 225°C, pKb -1.2) AD: 10-amino-1-decanol (primary aliphatic amine, boiling point 269°C, pKb -1.2) ADD: 12-amino-1-dodecanol (primary aliphatic amine, boiling point 304°C, pKb -1.2) HMDA: Hexamethylenediamine DAPA: 3,3'-diaminodipropylamine HA-PTS: Hexylammonium p-toluenesulfonate (amine salt having a cationic species with a primary aliphatic amine structure and an anionic species which is a sulfonate ion) AN-PTS: anilinium p-toluenesulfonate (an amine salt having a cationic species with a primary aromatic amine structure and an anionic species that is a sulfonate ion)

[0189] <(c) Photoacid Generator> PAG-103: "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene, maximum absorption wavelength: 405 nm, molecular weight: 348, manufactured by BASF Japan Ltd.) <Solvent> CP: cyclopentanone

[0190] <Compounds containing fluorine element> Fc-1: 2,2-bis(4-hydroxyphenyl)hexafluoropropane FI-1: (decyltriethyl)ammonium fluoride.

[0191] (1) Weight-average molecular weight The weight-average molecular weight (Mw) in terms of polystyrene was measured using a GPC analyzer under the following conditions: Measuring device: Waters 2695 (manufactured by Waters Corporation) Column temperature: 50°C Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21 wt% lithium chloride and 0.48 wt% phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).

[0192] (2) Phenol equivalent and carboxylic acid equivalent The phenol value (unit: mgKOH / g) or carboxylic acid value (unit: mgKOH / g) was measured by potentiometric titration using an automatic potentiometric titrator (AT-510; manufactured by Kyoto Electronics Manufacturing Co., Ltd.) and a 0.1 mol / L sodium hydroxide / ethanol solution as a titration reagent and a xylene / N,N-dimethylformamide = 1 / 1 (mass ratio) as a titration solvent in accordance with "JIS K2501 (2003)." The phenol equivalent (unit: g / mol) or carboxylic acid equivalent (unit: g / mol) was calculated from the measured phenol value or carboxylic acid value.

[0193] When the composition contained multiple resins having phenolic hydroxyl groups or carboxyl groups, separable components in the composition were removed by methods such as centrifugation, liquid-liquid separation, and column chromatography, and then each resin was separated by GPC fractionation. Thereafter, the carboxylic acid equivalent (unit: g / mol) was calculated based on the above-mentioned method for measuring the phenol equivalent or carboxylic acid equivalent.

[0194] (3) Imide Ring Closure Rate and Benzoxazole Ring Closure Rate of Resin Regarding the imide ring closure rate, each of the above resins was dissolved in GBL to a concentration of 35% by mass to prepare a resin solution. Each of the resulting resin solutions was applied to a silicon wafer using a spin coater (1H-DX; manufactured by Mikasa Co., Ltd.) and then baked at 120 ° C for 180 seconds to produce a resin film with a thickness of 4 to 5 μm. The prepared silicon wafer with the resin film was divided into two, and one of the two was heated in a clean oven (CLH-21CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) at 140 ° C for 30 minutes in a nitrogen atmosphere with an oxygen concentration of 20 ppm by mass or less, and then further heated to 320 ° C for 60 minutes to completely close the imide ring (resin film after heating). The other half was used as is without heat treatment (resin film before heating). Using an infrared spectrophotometer (FT-720; manufactured by Horiba, Ltd.), the transmission infrared absorption spectra of the resin film before and after heating were measured. The absorption peak of the imide structure due to polyimide (1,780 cm －１ Near 1,377 cm －１ After confirming the presence of 1,377 cm before heating, －１ Peak intensity (X) near 1,377 cm after heating －１ The peak intensity (Y) around each of the points was determined. The imide ring closure rate in the resin film before heating was calculated using the following formula: Imide ring closure rate [%] = (X / Y) x 100.

[0195] Regarding the benzoxazole ring closure rate, a resin film with a thickness of 4 to 5 μm was prepared using the same method as above. The prepared silicon wafer with the resin film was divided into two, and one half was heated at 320°C for 30 minutes using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation) to completely close the benzoxazole ring (resin film after heating). The other half was used as is without being heated (resin film before heating). Using an infrared spectrophotometer (FT-720; manufactured by HORIBA, Ltd.), the transmission infrared absorption spectra of the resin film before and after heating were measured. The absorption peak (1,570 cm) of the benzoxazole structure due to polybenzoxazole was measured. －１ After confirming the presence of a peak due to C=C (C=N) stretching vibration near 1,570 cm before heating, －１ Peak intensity (P) near 1,570 cm after heating －１ The peak intensity (Q) around each peak was determined. The benzoxazole ring closure rate in the resin film before heating was calculated using the following formula: Benzoxazole ring closure rate [%] = (P / Q) x 100.

[0196] (4) Molar Ratio of Polyimide Units, etc. Each of the above resins was separated by GPC fractionation before use. The resins in the compositions were extracted with dichloromethane, ultracentrifuged, and then separated from the dichloromethane-insoluble matter by GPC fractionation before use. Each resin was analyzed by methods such as proton nuclear magnetic resonance spectroscopy, infrared spectroscopy, pyrolysis gas chromatography-mass spectrometry, and reactive pyrolysis gas chromatography-mass spectrometry. From the obtained measurement results, the structures of the polyimide unit (imide structure), polyimide precursor unit (amidic acid structure and amic acid ester structure), polybenzoxazole unit (benzoxazole structure), polybenzoxazole precursor unit (hydroxyamide structure), and polyamideimide unit (imide structure and amide structure), as well as the copolymerization monomers that constitute them, were determined. Next, each copolymerization monomer was prepared as a standard sample, and peaks unique to each copolymerization monomer were confirmed by proton nuclear magnetic resonance spectroscopy. The molar ratio of each unit in the resin to the copolymerization monomers that constitute it was then calculated from the area ratio of the peaks in the proton nuclear magnetic resonance spectroscopy spectrum of each resin.

[0197] (5) Content of specific elements in resin or composition The content of fluorine element in the resin or composition was measured by combustion ion chromatography under the following measurement conditions. The resin and the resin in the composition were used after separation by GPC fractionation or by dichloromethane extraction, ultracentrifugation, and GPC fractionation. The resin or composition was burned and decomposed in the combustion tube of the analyzer, and the generated gas was absorbed in an absorption liquid, after which a portion of the absorption liquid was analyzed by ion chromatography. The content of fluorine element in the total solid content of the composition was calculated from the obtained measurement value and the following formula.

[0198] (Content of specific element relative to total solid content of composition) = (Content of specific element in composition) × 100 / (Solid content concentration of composition [mass %])

[0199] <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C, Outlet 1000°C Gas: Ar / O ２ 200mL / min, O ２ 400 mL / min Absorption liquid: H ２ O ２ 0.1 mass% Absorption amount: 5 mL

[0200] <Conditions for Ion Chromatography and Anion Analysis> System: ICS1600 (manufactured by DIONEX) Mobile phase: 2.7 mmol / L Na ２ CO ３ , 0.3 mmol / L NaHCO ３ Flow rate: 1.50 mL / min Detector: electrical conductivity detector Injection volume: 100 μL.

[0201] (6) Preparation of Relief Pattern The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coater / developer (manufactured by Tokyo Electron Limited), and heated at 100°C for 2 minutes to prepare a photosensitive resin film with a film thickness of 4.0 μm. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. Thereafter, using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), the film was exposed to light at an exposure dose of 5 to 300 mJ / cm through a mask having a pattern of 10 μm contact holes. ２ in the range of 5 mJ / cm ２ After exposure, the film was heated at 170°C for 30 minutes, and developed for 80 seconds using the ACT-8 developing device with 2.38% by mass of TMAH (manufactured by Tama Chemicals Co., Ltd.) as a developer, followed by rinsing with distilled water, shaking off, and heating at 310°C for 10 minutes to obtain a relief pattern.

[0202] (6-1) Calculation of the amount of film reduction after development The amount of film reduction after development was calculated by subtracting the film thickness after development from the film thickness in the unexposed area before development. The results were judged as follows, and A+ to B, where the amount of film reduction was less than 0.4 μm, was considered to be acceptable. A+: The amount of film reduction after development was less than 0.15 μm A: The amount of film reduction after development was 0.15 μm or more but less than 0.2 μm B+: The amount of film reduction after development was 0.2 μm or more but less than 0.3 μm B: The amount of film reduction after development was 0.3 μm or more but less than 0.4 μm C: The amount of film reduction after development was 0.4 μm or more.

[0203] (6-2) Sensitivity The resulting relief pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the sensitivity. The results were judged as follows, and a sensitivity of 200 mJ / cm was determined. ２ A+: Sensitivity is less than 85 mJ / cm ２ A: Sensitivity is less than 85 mJ / cm ２ Above, 100mJ / cm ２ A-: Sensitivity is less than 100 mJ / cm ２Above, 120mJ / cm ２ B+: Sensitivity is less than 120 mJ / cm ２ Above, 140mJ / cm ２ B: Sensitivity is less than 140 mJ / cm ２ Above, 170mJ / cm ２ B-: Sensitivity is less than 170 mJ / cm ２ Above, 200mJ / cm ２ C: Sensitivity is less than 200 mJ / cm ２ That's all.

[0204] (7) Glass Transition Temperature Using a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Inc., a nitrogen flow rate of 40 mL / min was set, and liquid nitrogen was used for cooling. 5 mg of the cured product recovered from the resulting relief pattern was weighed into an aluminum pan, and the calorific value was measured using an empty aluminum pan as a reference, according to the following program sequence: (3-1) After adjusting to 30°C, the temperature was increased from 30°C to 100°C at a rate of 10°C / min. (3-2) The temperature was maintained at 100°C for 5 minutes. (3-3) The temperature was increased from 100°C to 500°C at a rate of 10°C / min.

[0205] In the above (3-3), if a baseline shift was observed, the temperature at the intersection of the low-temperature baseline and the tangent line at the inflection point was taken as the glass transition temperature. The results were judged as follows, and A+ to B, which indicate a glass transition temperature of 200°C or higher, were considered to be acceptable. A+: Glass transition temperature of 350°C or higher A: Glass transition temperature of 300°C or higher but lower than 350°C B+: Glass transition temperature of 250°C or higher but lower than 300°C B: Glass transition temperature of 200°C or higher but lower than 250°C C: Glass transition temperature lower than 200°C.

[0206] (8) Amount of (b) amine compound remaining in the cured film The cured product recovered from the resulting relief pattern was measured by gas chromatography using the following apparatus configuration and measurement conditions to measure the fragment intensity of the (b) amine compound. Separately, a calibration curve relating the amount of (b) amine compound added and the fragment intensity was prepared, and the amount of (b) amine compound remaining in the cured product was evaluated.

[0207] [Device configuration] Agilent 6890 / 5973N, Japan Analytical Industry Curie Point Pyrolyzer JHP-3S G / C column: Agilent HP-5ms 30m non-polar (capillary column with polydimethylsiloxane as the fixed layer)

[0208] [Measurement conditions] Carrier gas: He (80 MPa) Pyrolysis: Sample heated to 400°C (decomposition chamber temperature 280°C) Column chamber: After holding at 40°C for 5 minutes, heated to 350°C at a temperature increase rate of 10°C / min and held at 350°C for 20 minutes Mass spectrometry: Electron impact ionization (EI), ionization voltage 70 eV, ionization chamber temperature 200°C Quadrupole mass selection, quadrupole chamber temperature 150°C.

[0209] Synthesis Example 1: Synthesis of Polyimide Precursor (PA-1), a Polyamide Under a dry nitrogen stream, 18.42 g (100 mmol) of DABP as a diamine and 180 g of NMP were weighed and dissolved in a four-neck flask. To this was added 26.48 g (90 mmol) of BPDA as an acid dianhydride along with 40 g of NMP, and the mixture was stirred at 40°C for 1 hour. Next, 2.96 g (20 mmol) of phthalic anhydride was added along with 40 g of NMP, and the mixture was reacted at 40°C for 1 hour, followed by stirring at 200°C for 4 hours. After stirring, the solution was poured into 2 L of pure water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 40°C for 4 hours to obtain a powder of polyimide precursor (PA-1), a polyamide. The resulting resin had an Mw of 27,400 and an acid equivalent of 240 g / mol.

[0210] Synthesis Examples 2 to 3: Synthesis of polyimide precursors (PA-2 to 3), which are polyamides

[0073] Synthesis was performed in the same manner as in Synthesis Example 1, except that the types and amounts of the amine derivative, carboxylic acid derivative, and end-capping agent used in Synthesis Example 1 were changed to those shown in Table 1. The Mw and acid equivalent of the resulting resins are shown in Table 1.

[0211] Synthesis Example 4 Synthesis of Polyimide Precursor (PA-4) (Polyamide) Under a dry nitrogen stream, 26.48 g (90 mmol) of BPDA as an acid dianhydride and 500 g of NMP were weighed and dissolved in a four-necked flask. 18.42 g (100 mmol) of DABP as a diamine was added thereto along with 50 g of NMP, and the mixture was stirred at 40°C for 2 hours. Next, 2.96 g (20 mmol) of phthalic anhydride was added together with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 23.8 g (200 mmol) of N,N-dimethylformamide dimethyl acetal (DFA) with 50 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was poured into 2 L of pure water, and a white precipitate was obtained. The precipitate was collected by filtration, washed three times with pure water, and then dried for 24 hours in a vacuum dryer at 80°C to obtain a powder of polyimide precursor (PA-4), which was a polyamide. The resulting resin had an Mw of 27,000 and an acid equivalent of 440 g / mol.

[0212] Synthesis Examples 5 and 6: Synthesis of polyimide precursors (PA-5 and PA-6), which are polyamides

[0073] Synthesis was performed in the same manner as in Synthesis Example 4, except that the types and amounts of the amine derivative, carboxylic acid derivative, end-capping agent, and esterifying agent used in Synthesis Example 4 were changed to those shown in Table 1. The Mw and acid equivalent of the resulting resins are shown in Table 1.

[0213] Synthesis Example 7: Synthesis of Polyimide (PI-1) Under a dry nitrogen stream, 18.42 g (100 mmol) of DABP as a diamine and 180 g of NMP were weighed and dissolved in a four-neck flask. To this was added 26.48 g (90 mmol) of BPDA as an acid dianhydride along with 40 g of NMP, and the mixture was stirred at 40°C for 1 hour. Next, 2.96 g (20 mmol) of phthalic anhydride was added along with 40 g of NMP, and the mixture was reacted at 40°C for 1 hour, followed by stirring at 200°C for 4 hours. After stirring, the solution was poured into 2 L of pure water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 200°C for 4 hours to obtain a powder of polyimide (PI-1). The resulting resin had an Mw of 27,800 and an acid equivalent of 2,500 g / mol.

[0214] Synthesis Example 8 Synthesis of Polyimide (PI-2) Synthesis was performed in the same manner as in Synthesis Example 7, except that the types and amounts of the amine derivative, carboxylic acid derivative, and end-capping agent used in Synthesis Example 7 were changed to those shown in Table 1. The Mw and acid equivalent of the resulting resin are shown in Table 1.

[0215] Synthesis Example 9: Synthesis of Polybenzoxazole Precursor (PA-7), a Polyamide Under a dry nitrogen stream, 180 mmol of a mixture of dicarboxylic acid derivatives obtained by reacting 4,4'-biphenyldicarboxylic acid (180 mmol) with 1-hydroxy-1,2,3-benzotriazole (360 mmol) was dissolved in 570 g of NMP, DABP (130 mmol), and DADHBP (70 mmol) and the reaction was allowed to proceed at 75°C for 12 hours. Next, phthalic anhydride (40 mmol) dissolved in 70 g of NMP was added, and the mixture was stirred for an additional 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a water / methanol solution (3 / 1 by volume) to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the desired alkali-soluble resin (a-8) consisting of a polybenzoxazole precursor. A powder of polybenzoxazole precursor (PA-7), a polyamide, was obtained. The resulting resin had a Mw of 25,000 and an acid equivalent of 460 g / mol.

[0216] Synthesis Example 10: Synthesis of polybenzoxazole precursor (PA-8), a polyamide

[0123] Synthesis was performed in the same manner as in Synthesis Example 9, except that the types and amounts of the amine derivative, carboxylic acid derivative, and end-capping agent used in Synthesis Example 9 were changed to those shown in Table 1. The Mw and acid equivalent of the resulting resin are shown in Table 1.

[0217] Synthesis Example 11: Synthesis of Polybenzoxazole (PBO-1) Under a dry nitrogen stream, 21.62 g (100 mmol) of DADHBP was dissolved in 75 g of NMP. The solution was then cooled to -15°C, and a solution of 34.89 g (125 mmol) of BPDCC dissolved in 30 g of NMP was added dropwise so that the temperature in the reaction system did not exceed 0°C. After the dropwise addition was completed, stirring was continued for 6 hours at 20°C. After the reaction was completed, the above solution was poured into 3 L of pure water containing 10 wt% methanol to precipitate a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 200°C for 4 hours to obtain polybenzoxazole (PBO-1). The resulting resin had an Mw of 18,700 and an acid equivalent of 450 g / mol.

[0218] Synthesis Example 12 Synthesis of polybenzoxazole (PBO-2) Synthesis was performed in the same manner as in Synthesis Example 11, except that the types and amounts of the amine derivative, carboxylic acid derivative, and end-capping agent used in Synthesis Example 11 were changed to those shown in Table 1. The Mw and acid equivalent of the resulting resin are shown in Table 1.

[0219] Synthesis Example 13: Synthesis of polyamideimide (PAI-1) Synthesis Example 13 was synthesized by a known method based on the method described in Synthesis Example 9 in paragraph

[0160] of WO 2018 / 159384, with appropriate changes to the monomer compounds to be used as monomers and the copolymerization ratio. The amine derivative, carboxylic acid derivative, and end-capping agent were as shown in Table 1, and the Mw and acid equivalent of the obtained resin were also shown in Table 1.

[0220]

[0221] Example 1 Under yellow light, (a) 2.50 g of PA-1 as a resin, (b) 2.50 g of HA as an amine compound, (c) 0.20 g of PAG-103 as a photoacid generator, and 30 g of CP as a solvent were added and stirred to prepare a photosensitive resin composition.

[0222] (2) Relief patterns were formed on the prepared photosensitive resin compositions, and (2-1) developed film weight loss, (2-2) sensitivity, (3) glass transition temperature, and (4) remaining amount of (b) amine compound in the cured film were evaluated. The evaluation results are shown in Tables 2 and 3.

[0223] Examples 2 to 36 and Comparative Examples 1 to 4 Evaluations were performed in the same manner as in Example 1, except that the types and amounts of (a) resin, (b) amine compound, (c) photoacid generator, and CP in the photosensitive resin composition were changed to those shown in Tables 2 and 3. The evaluation results are shown in Tables 2 and 3. In Examples 33 to 36, the fluorine-containing compounds Fc-1 and F-I-1 were added so that the content of fluorine in the total solid content of the photosensitive resin composition was the content shown in Table 3. In Examples 1 to 32 and Comparative Examples 1 to 4, the content of fluorine in the total solid content of the photosensitive resin composition was 0 ppm by mass.

[0224] In Comparative Example 1, the content of the (b) amine compound does not satisfy the requirements for the invention. In Comparative Example 2, the (b) amine compound does not contain a primary amine or a secondary amine. Therefore, it is clear that Comparative Examples 1 and 2 are inferior in various properties. Furthermore, in Comparative Examples 3 and 4, the photosensitive resin composition does not contain the (b) amine compound or the (c) photoacid generator. Therefore, it is clear that Comparative Examples 3 and 4 cannot form a pattern, and do not achieve the effects of the invention.

[0225]

[0226]

[0227] The present invention is suitable for application to a highly sensitive photosensitive resin composition which has excellent heat resistance, little film loss during development, and high sensitivity.

Claims

1. A photosensitive resin composition comprising: (a) one or more resins selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, and precursors thereof (hereinafter referred to as "(a) resin"); (b) an amine compound; and (c) a photoacid generator, wherein the (b) amine compound is a primary amine or a secondary amine, and the (b) amine compound is contained in an amount of 35 parts by mass or more per 100 parts by mass of the (a) resin.

2. The photosensitive resin composition according to claim 1, wherein the acid equivalent of the resin (a) is 500 g / mol or more, and the carboxylic acid equivalent of the resin (a) is 500 g / mol or more, or the resin (a) does not have a carboxy group.

3. The photosensitive resin composition according to claim 2, wherein the (a) resin contains an amide bond in a repeating unit and is a polyimide precursor, a polyamideimide precursor or a polybenzoxazole precursor.

4. The photosensitive resin composition according to claim 3, wherein the (a) resin has an electron-withdrawing group, and the electron-withdrawing group is one or more groups selected from the group consisting of a nitro group, a cyano group, a sulfo group, and a sulfonyl group.

5. The photosensitive resin composition according to claim 1, wherein the amine compound (b) is a monoamine compound.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the amine compound (b) is a primary amine.

7. The photosensitive resin composition according to any one of claims 1 to 5, wherein the amine compound (b) is an aliphatic amine.

8. The photosensitive resin composition according to any one of claims 1 to 5, wherein the amine compound (b) has a pKb of 6 or less.

9. The photosensitive resin composition according to any one of claims 1 to 5, wherein the boiling point of the amine compound (b) at 1 atmospheric pressure is 100°C or higher and 300°C or lower.

10. The photosensitive resin composition according to claim 1, wherein the (a) resin has an electron-withdrawing group, and the (a) resin comprises one or more resins selected from the group consisting of: (a1) a polyimide or polyamideimide containing a structural unit represented by formula (1) (hereinafter referred to as "(a1) resin"); (a2) a polyimide precursor or polyamideimide precursor containing a structural unit represented by formula (2) (hereinafter referred to as "(a2) resin"); (a3) ​​a polyamideimide containing a structural unit represented by formula (3) (hereinafter referred to as "(a3) resin"); (a4) a polybenzoxazole containing a structural unit represented by formula (4) (hereinafter referred to as "(a4) resin"); and (a5) a polybenzoxazole precursor containing a structural unit represented by formula (5) (hereinafter referred to as "(a5) resin"). (In formula (1), L １ is a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. １ , X １ ~X ４ and X ５ ~X ８ X ｎ (n=1 to 8) are C-R ｎ (n = 1 to 8). ｎ (n=1 to 8) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. １ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ (n=2-3, 6-7) at least one of which has an electron-withdrawing group. * indicates a bonding site.) (In formula (2), L ２ is a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. ２ , X １１ ~X １４ and X １５ ~X １８ X ｎ (n=11 to 18) are C-R ｎ (n = 11 to 18). ｎ (n=9 to 18) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ２ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ (n=12-13, 16-17) at least one of which has an electron-withdrawing group. * indicates a bonding site.) (In formula (3), L ３ is an amide bond. ３ , X １９ ~X ２２ X ｎ (n=19-22) are C-R ｎ (n=19 to 22). ｎ (n=19 to 22) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ｎ (n=20 to 21) at least one of which has an electron-withdrawing group. * indicates a bonding site.) (In formula (4), L ４ is a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. ４ , X ３１ ~X ３５ and X ３６ ~X ４０ X ｎ (n=23-40) are C-R ｎ (n=23 to 40). ｎ (n=23 to 40) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ４ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=33, 38) has an electron-withdrawing group. １ , X ２３ ~X ２６ It is linked to one of the positions. ２ , X ２７ ~X ３０ It is linked to one of the positions. １ and * ２ indicates the binding site.) (In formula (5), L ５ is a single bond, a sulfonyl group, >C(CF ３ ) ２ , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms. ５ , X ４９ ~X ５３ and X ５４ ~X ５８ X ｎ (n=41 to 58) are C-R ｎ (n=41 to 58). ｎ (n=41 to 58) are each independently a group selected from the group consisting of a hydrogen atom, an electron-withdrawing group, and a monovalent organic group having 1 to 20 carbon atoms. ５ Even if the sulfonyl group is >C(CF ３ ) ２ If not, R ｎ At least one of (n=51, 58) has an electron-withdrawing group. ３ , X ４１ ~X ４４ It is linked to one of the positions. ４ , X ４５ ~X ４８ It is linked to one of the positions. ３ and * ４ indicates the binding site.) 11. When the (a) resin contains the (a1) resin, R ｎ (n=1 to 8), any one or more of which has an electron-withdrawing group, and when the (a) resin has an (a2) resin, R ｎ (n=11 to 18), any one or more of which has an electron-withdrawing group, and when the (a) resin has an (a3) ​​resin, R ｎ (n=19 to 22), any one or more of which has an electron-withdrawing group, and when the (a) resin has an (a4) resin, R ｎ (n=23 to 40), any one or more of which has an electron-withdrawing group, and when the (a) resin has an (a5) resin, R ｎ The photosensitive resin composition according to claim 10, wherein at least one of (n=41 to 58) has an electron-withdrawing group.

12. The photosensitive resin composition according to any one of claims 1 to 5, 10 and 11, which satisfies at least one of the following conditions (P1α) and (1α): (P1α) (a) the content of fluorine element in the resin structure is 10,000 mass ppm or less (1α) the content of fluorine element in the total solid content of the photosensitive resin composition is 1,000 mass ppm or less 13. The photosensitive resin composition according to any one of claims 1 to 5, 10 and 11, wherein the (b) amine compound is an amine salt, and the amine salt is a compound containing a cationic species having a primary amine structure or a secondary amine structure, and an anionic species.

14. A method for producing a pattern, comprising the steps of: applying the photosensitive resin composition according to any one of claims 1 to 5, 10 and 11 to a substrate; exposing the applied product through a photomask; heating the applied product simultaneously with or after the exposure through the photomask; developing the applied product after heating; and heating the applied product after development.

15. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5, 10 and 11.

16. The cured product according to claim 15, wherein the content of the amine compound (b) in the cured product is 0.001 mass % or more and 1.00 mass % or less, relative to 100 mass % of the cured product.

17. An electronic part comprising the cured product according to claim 15.

18. A display device comprising the cured product according to claim 15.

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