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

Abstract

The purpose of the present invention is to provide a photosensitive resin composition having excellent heat resistance, low film reduction during development, and high sensitivity. The present invention is a photosensitive resin composition containing (a) one or more resins (hereinafter referred to as "(a) resins") selected from the group consisting of polyimides, polyamideimides, polybenzoxazoles, and precursors thereof, (b) an amine compound, and (c) a photoacid generator, the amine compound (b) being a primary amine or a secondary amine, the amine compound (b) is contained in an amount of 35 parts by mass or more per 100 parts by mass of the resin (a).

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a method for manufacturing a pattern, a cured material, electronic components, and a display device. Background Technology

[0002] For surface protective films or interlayer insulating films used in electronic components, insulating layers of organic electroluminescent elements, or planarization films of thin-film transistor (TFT) substrates, polyimides or polybenzoxazoles, which possess excellent heat resistance, electrical insulation, and mechanical properties, are widely used. In recent years, photosensitive resin compositions that impart photosensitive properties to these resins themselves or their precursors have been widely used. Using photosensitive resin compositions simplifies patterning processes and shortens complex manufacturing steps.

[0003] Regarding photosensitive resin compositions, there are positive materials where the exposed portion is easily soluble in the developer and can be patterned, and negative materials where the composition itself is easily soluble and the exposed portion is insoluble in the developer.

[0004] As a positive type of photosensitive resin composition, photosensitive resin compositions are known, for example, those formed by adding a quinone diazide compound to polyimide, polyamide-imide, polybenzoxazole, and their precursors (see, for example, Patent Document 1). As a negative type of photosensitive resin composition, photosensitive resin compositions are known, for example, those formed by adding a photopolymerizable compound and a photopolymerization initiator to polyimide, polyamide-imide, polybenzoxazole, and their precursors (see, for example, Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2011-180473

[0008] Patent Document 2: Japanese Patent Application Publication No. 2021-120714 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] In recent years, with the advancement of high integration and large size of semiconductor devices, there are requirements for thinner, smaller, and more uniform film thickness of sealing resin packages. This has gradually led to a need for resins with higher sensitivity, better heat resistance, and reduced film thickness reduction during development compared to the past.

[0011] However, the technology described in Patent Document 1 has the following problems: the difference in dissolution contrast between the unexposed material and the exposed part is small, and there is a limit to the reduction in film thickness during development; or the heat resistance is reduced due to the residual quinone diazide compound in the developed film.

[0012] Furthermore, in the technology described in Patent Document 2, the use of (meth)acrylate as a photopolymerization initiator results in a decrease in heat resistance.

[0013] The purpose of this invention is to provide a photosensitive resin composition with excellent heat resistance, minimal film reduction during development, and high sensitivity.

[0014] Technical means to solve the problem

[0015] In order to solve the aforementioned problem, the photosensitive resin composition of the present invention has the following structures [1] to

[18] .

[0016] [1] A photosensitive resin composition comprising:

[0017] (a) One or more resins selected from the group consisting of polyimides, polyamide-imides, polybenzoxazoles, and precursors thereof (hereinafter referred to as "(a) resins")

[0018] (b) amine compounds, and

[0019] (c) Photoacid generator,

[0020] The amine compound in (b) is a primary or secondary amine.

[0021] The photosensitive resin composition contains at least 35 parts by mass of the amine compound (b) relative to 100 parts by mass of the resin (a).

[0022] [2] According to the photosensitive resin composition described in [1], wherein the acid equivalent of the resin (a) is 500 g / mol or more, and

[0023] The resin in (a) has a carboxylic acid equivalent of 500 g / mol or more, or the resin in (a) does not have a carboxyl group.

[0024] [3] According to the photosensitive resin composition described in [1] or [2], wherein the (a) resin is a resin containing an amide bond in the repeating unit and is a polyimide precursor, a polyamide-imide precursor or a polybenzoxazole precursor.

[0025] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the (a) resin has an electron-withdrawing group, the electron-withdrawing group being one or more groups selected from the group consisting of nitro, cyano, sulfon, and sulfonyl.

[0026] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (b) amine compound is a monoamine compound.

[0027] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the (b) amine compound is a primary amine.

[0028] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the (b) amine compound is an aliphatic amine.

[0029] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the pKb of the (b) amine compound is 6 or less.

[0030] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the boiling point of the (b) amine compound at 1 atmosphere is above 100°C and below 300°C.

[0031]

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the (a) resin has an electron-withdrawing group, and the (a) resin comprises selected from

[0032] (a1) includes the polyimide or polyamide-imide (hereinafter referred to as "(a1) resin") that is a constituent unit represented by formula (1).

[0033] (a2) includes the polyimide precursor or polyamide-imide precursor of the constituent unit represented by formula (2) (hereinafter referred to as "(a2) resin").

[0034] (a3) includes the polyamide-imide (hereinafter referred to as "(a3) resin") that is the constituent unit represented by formula (3).

[0035] (a4) includes the polybenzoxazole (hereinafter referred to as "(a4) resin"), which is a constituent unit represented by formula (4), and

[0036] (a5) includes the polybenzoxazole precursor of the constituent unit represented by formula (5) (hereinafter referred to as "(a5) resin")

[0037] One or more resins in the group.

[0038] [Chemistry 1]

[0039]

[0040] In equation (1), L 1 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 1 In X 1 ~X 4 Any position in, and X 5 ~X 8 Connect at any point in X. n (n=1~8) are CR n (n=1~8). R n (n=1~8) are groups independently selected from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 1 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=2~3, 6~7) have electron-withdrawing groups. Indicates the bonding location.

[0041] [Chemistry 2]

[0042]

[0043] In equation (2), L 2 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 2 In X 11 ~X 14 Any position in, and X 15 ~X 18 Connect at any point in X. n (n=11~18) are CR n (n=11~18). R n (n=9~18) are groups independently selected from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 2 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=12~13, 16~17) have electron-withdrawing groups. Indicates the bonding location.

[0044] [Chemistry 3]

[0045]

[0046] In equation (3), L 3 It is an amide bond. L 3 With X19 ~X 22 Link to any position in X. n (n=19~22) are CR n (n=19~22). R n (n=19~22) are groups selected independently from the group consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. R n One or more of the ones in (n=20~21) have electron-withdrawing groups. Indicates the bonding location.

[0047] [Chemistry 4]

[0048]

[0049] In equation (4), L 4 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 4 In X 31 ~X 35 Any position in, and X 36 ~X 40 Connect at any point in X. n (n=23~40) are CR n (n=23~40). R n (n=23~40) are groups independently selected from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 4 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=33, 38) have electron-withdrawing groups. 1 With X 23 ~X 26 Link any position in the string. 2 With X 27 ~X 30 Link any position in the string. 1 and 2 Indicates the bonding location.

[0050] [Chemistry 5]

[0051]

[0052] In equation (5), L 5 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 5 In X49 ~X 53 Any position in, and X 54 ~X 58 Connect at any point in X. n (n=41~58) are CR n (n=41~58). R n (n=41~58) are groups selected independently from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 5 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of (n=51, 56) have electron-withdrawing groups. 3 With X 41 ~X 44 Link any position in the string. 4 With X 45 ~X 48 Link any position in the string. 3 and 4 Indicates the bonding location.

[0053]

[11] According to the photosensitive resin composition described in

[10] , wherein when the (a) resin has the (a1) resin, R n Any one or more of the groups (n=1~8) have electron-withdrawing groups.

[0054] In the case where resin (a) has resin (a2), R n Any one or more of the groups (n=11~18) have electron-withdrawing groups.

[0055] In the case where resin (a) has resin (a3), R n Any one or more of the groups (n=19~22) have electron-withdrawing groups.

[0056] In the case where resin (a) has resin (a4), R n Any one or more of the groups (n=23~40) have electron-withdrawing groups.

[0057] In the case where resin (a) has resin (a5), R n One or more of the ones in (n=41~58) have electron-withdrawing groups.

[0058]

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

[11] , wherein at least one of the following conditions (P1α) and the following conditions (1α) are satisfied.

[0059] (P1α) The content of fluorine in the structure of (a) resin is less than 10,000 ppm by mass.

[0060] (1α) The content of fluorine in all solid components of the photosensitive resin composition is less than 1,000 ppm by mass.

[0061]

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

[12] , wherein the (b) amine compound is an amine salt,

[0062] The amine salt is a compound containing a cationic species having a primary amine structure or a secondary amine structure, as well as an anionic species.

[0063]

[14] A method for manufacturing a pattern, comprising:

[0064] The process of applying the photosensitive resin composition according to any one of [1] to

[13] onto a substrate;

[0065] The process of exposing the coated material to a light-blocking mask;

[0066] The process of heating the coated material during or after exposure of the photomask;

[0067] The process of developing the heated coating; and

[0068] The process of heating the developed coating.

[0069]

[15] A hardened material is formed by hardening a photosensitive resin composition according to any one of [1] to

[13] .

[0070]

[16] According to the hardened material described in

[15] , the content of (b) amine compound in the hardened material is more than 0.001% by mass and less than 1.00% by mass relative to 100% by mass of the hardened material.

[0071]

[17] An electronic component having a hardened material as described in

[15] or

[16] .

[0072]

[18] A display device having a hardened material as described in

[15] or

[16] .

[0073] The effects of the invention

[0074] The photosensitive resin composition of the present invention exhibits minimal film thickness reduction during development and excellent sensitivity and heat resistance. Detailed Implementation

[0075] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented by various modifications according to the purpose or use.

[0076] The photosensitive resin composition of the present invention comprises: (a) one or more resins selected from the group consisting of polyimide, polyamide-imide, 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 or secondary amine, and the photosensitive resin composition contains 35 or more parts by weight of the (b) amine compound relative to 100 parts by weight of the (a) resin.

[0077] The photosensitive resin composition of the embodiments of the present invention contains (c) a photoacid generator, thus, by irradiating with exposure light corresponding to the photoacid generator contained therein, acid can be generated in the composition. In the exposed portion, the generated acid acts as a catalyst, reacting with (b) an amine compound through (a) resin, thereby reducing the molecular weight of (a) resin and making it soluble in the developer. Therefore, the photosensitive resin composition of the embodiments of the present invention can exhibit a solubility contrast relative to the developer in the unexposed portion and the exposed portion, with the exposed portion dissolving to form a raised pattern.

[0078] <(a) Resin>

[0079] The photosensitive resin composition of embodiments of the present invention comprises: (a) one or more resins selected from the group consisting of polyimides, polyamide-imides, polybenzoxazoles, and precursors thereof (hereinafter referred to as "(a) resin"). Among these, (a) resin is preferably selected from the group consisting of polyimides, polyamide-imides, and polyamides, with regard to high reactivity with (b) amine compounds. In addition, (a) resin is also preferably polyamide from the viewpoint of improving sensitivity. In the present invention, (a) resin is more preferably a polyimide precursor, a polyamide-imide precursor, or a polybenzoxazole precursor from the viewpoint of improving reactivity with (b) amine compounds and improving sensitivity.

[0080] Polyimide is a polymer containing imide bonds in repeating units. Polyimides can be synthesized using known methods. For example, resins obtained by reacting a tetracarboxylic acid, its corresponding tetracarboxylic dianhydride or tetracarboxylic acid diester dichloride, etc., with a diamine, its corresponding diisocyanate compound, or trimethylsilyl diamine, etc., can be dehydrated and ring-closed by heating or using a catalyst such as an acid or base. Therefore, polyimides have tetracarboxylic acid and / or its derivative residues, and diamine and / or its derivative residues.

[0081] Polyamide-imide is a polymer containing amide and imide bonds in repeating units. Polyamide-imide can be synthesized using known methods. For example, resins obtained by reacting a compound obtained by substituting a portion of the hydrogen atoms on the benzene ring of trimellitic acid chloride, the corresponding trimellitic anhydride chloride, or such compounds with a nitro, amino, or sulfonyl group, with a diamine, the corresponding diisocyanate compound, or trimethylsilyldiamine, can be dehydrated and ring-closed by heating or by a reaction using a catalyst such as an acid or base.

[0082] Polybenzoxazole is a polymer containing a benzoxazole structure in its repeating unit. Polybenzoxazole can be synthesized using known methods. For example, resins obtained by reacting a diaminophenol compound with a dicarboxylic acid or its corresponding chloride or reactive ester can be dehydrated and cyclic-closed by heating or using a catalyst such as an acid, base, acetic anhydride, or carbodiimide compound. Therefore, polybenzoxazole contains both dicarboxylic acid residues and diaminophenol residues.

[0083] Polyamide is a polymer containing amide bonds in repeating units. Polyamides can be synthesized using known methods. Polyamides are preferably polyimide precursors, polyamide-imide precursors, or polybenzoxazole precursors. In this invention, from the viewpoint of improving reactivity with (b) amine compounds and increasing sensitivity, (a) resin is more preferably a resin containing amide bonds in repeating units, and is a polyimide precursor, polyamide-imide precursor, or polybenzoxazole precursor.

[0084] The polyimide precursor is a polyamide that can be converted into polyimide by heating. Resin films with high heat resistance can be produced by containing the polyimide precursor. The polyimide precursor can be synthesized using known methods. For example, resins obtained by reacting a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride or tetracarboxylic acid diester dichloride, etc., with a diamine, the corresponding diisocyanate compound, or trimethylsilyldiamine, etc., can be listed.

[0085] The polyamide-imide precursor is a polyamide that can be converted into a polyamide-imide by heating. By containing the polyamide-imide precursor, resin films with high heat resistance can be produced. The polyamide-imide precursor can be synthesized using known methods. For example, resins obtained by reacting compounds formed by substituting a portion of the hydrogen atoms on the benzene ring of trimellitic acid chloride, the corresponding trimellitic anhydride chloride, or such compounds with a nitro, amino, or sulfonyl group, with a diamine, the corresponding diisocyanate compound, or trimethylsilyldiamine, etc.

[0086] The polybenzoxazole precursor is a polyamide that can be converted into polybenzoxazole by heating. Resin films with high heat resistance can be prepared by containing the polybenzoxazole precursor. The polybenzoxazole precursor can be synthesized using known methods. For example, resins obtained by reacting a diaminophenol compound with a dicarboxylic acid, the corresponding dicarboxylic acid chloride, or an active dicarboxylic acid ester can be cited.

[0087] Furthermore, polyamides can also be resins that are not equivalent to polyimide precursors, polyamide-imide precursors, or polybenzoxazole precursors. For example, resins obtained by reacting diamines, corresponding diisocyanate compounds, or trimethylsilyl diamines with dicarboxylic acids, corresponding dicarboxylic acid chlorides, or dicarboxylic acid reactive esters can be cited.

[0088] Examples of tetracarboxylic acids used in the synthesis of polyimides and polyimide precursors include: 1,2,3,4-cyclobutanetetracarboxylic acid, pyromellitic acid, 4,4'-biphenyltetracarboxylic acid, 4,4'-carbonyldiphthalic acid, 3,3',4,4'-biphenyl ethertetracarboxylic acid, 3,3',4,4'-biphenyl sulfonetetracarboxylic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, 2,2'-bis(3,4-dicarboxyphenyl)propionic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 4,4'-(9H-fluorene-9,9-diyl)diphthalic acid, and compounds formed by substituting a portion of the hydrogen atoms on the benzene ring of these with nitro, amino, sulfonyl, etc., but are not limited to these.

[0089] 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'-biphenyl ethertetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,2'-bis(3,4-dicarboxyphenyl)propionic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 5,5'-(9H-fluorene-9,9-diyl)bis(2-benzofuran-1,3-dione), and compounds formed by substituting a portion of the hydrogen atoms on the benzene ring of these compounds with nitro, amino, sulfonyl, etc., but are not limited to these.

[0090] Tetracarboxylic acid diester dichloride used in the synthesis of polyimide and polyimide precursors may include, for example, compounds formed by changing the carboxylic acid of a compound described as an example of the tetracarboxylic acid to an ester chloride, but are not limited to these.

[0091] Diamines used in the synthesis of polyimides, polyamide-imides, polyimide precursors, and polyamide-imide 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, and 3,3'-diamino-diphenyl sulfone. Phenyl 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-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-propyl dimethylsilyl)benzene, 3,7-diamino-2,8-dimethyldiphenyl sulfone, 9,9-bis(4-amino-phenyl)fluorene, and compounds formed by substituting a portion of the hydrogen atoms on the benzene ring of these compounds with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., but not limited to these.

[0092] Diisocyanate compounds used in the synthesis of polyimides, polyamide-imides, polyimide precursors, and polyamide-imide precursors may include, for example, compounds formed by changing the amino group of a compound described as an example of the diamine to an isocyanate group, but are not limited to these.

[0093] Trimethylsilyl diamine used in the synthesis of polyimides, polyamide-imides, polyimide precursors, and polyamide-imide precursors may be, for example, compounds in which a portion of the hydrogen atom on the benzene ring of a compound described as an example of said diamine is substituted with a trimethylsilyl group, but is not limited to these.

[0094] Examples of bisamino-phenolic compounds used in the synthesis of polybenzoxazole and its 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, and bis(3-amino-4-hydroxyphenyl) Propane, 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 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-benzamide)-4-hydroxyphenyl]hexafluoropropane, etc., but not limited to these.

[0095] Dicarboxylic acids used in the synthesis of polybenzoxazole and its precursors include, but are not limited to, terephthalic acid, isophthalic acid, dimeric acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, or sebacic acid.

[0096] The dicarboxylic acid chlorides used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, for example, compounds formed by changing the carboxylic acid of a compound described as an example of the dicarboxylic acid to a carboxylic acid chloride, but are not limited to these.

[0097] The dicarboxylic acid active esters used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, for example, compounds in which the carboxylic acid of a compound described as an example of the dicarboxylic acid is changed to a carboxylic acid active ester such as a thioester or a phenyl ester, but are not limited to these.

[0098] Furthermore, when the polyamide is a resin that is not equivalent to a polyimide precursor, a polyamide-imide precursor, or a polybenzoxazole precursor, the diamine, diisocyanate compound, trimethylsilyl diamine, dicarboxylic acid, dicarboxylic acid chloride, and dicarboxylic acid active ester used in the synthesis of such polyamide may be listed, but are not limited to these.

[0099] (a) The resin is preferably capped at the main chain ends by a known end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoreactive ester compound. Sealing the main chain ends with an end-capping agent improves the storage stability of the photosensitive resin composition. The proportion of the monoamine used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and more preferably 60 mol% or less, and more preferably 50 mol% or less, relative to all amine components constituting (a) resin. The proportion of the acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoreactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and more preferably 100 mol% or less, and more preferably 90 mol% or less, relative to the diamine component constituting (a) resin. Multiple different end groups can be introduced by reacting multiple end-capping agents.

[0100] Regarding (a) the weight-average molecular weight of the resin, for the purposes of suppressing the dissolution of the unexposed portion relative to the developer, improving mechanical properties, and heat resistance, it is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. For the purposes of improving the solubility of the exposed portion relative to the developer, it is preferably 100,000 or less, more preferably 60,000 or less, and even more preferably 30,000 or less. In this invention, the weight-average molecular weight is obtained by polystyrene conversion based on gel permeation chromatography using the method described later.

[0101] From the viewpoint of improving reactivity with (b) amine compounds, (a) resin is preferably having electron-withdrawing groups. To further improve the reactivity of (a) resin with (b) amine compounds, (a) resin is more preferably having two or more electron-withdrawing groups. (a) resin is further preferably having electron-withdrawing groups in repeating units.

[0102] In this invention, the term "electron-withdrawing group" refers to a group with a positive substituent constant σp0 value as defined in the 5th revised edition of the Handbook of Chemistry II-379 to II-380 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.). Specifically, examples include: halogen atoms, cyano groups, oxygen groups, carbonyl groups, carbonyloxy groups, oxycarbonyl groups, nitrile groups, sulfonyl groups, sulfinyl groups, sulfonyl groups, halogenated (cyclo)alkyl groups or halogenated aryl groups, and combinations thereof. Furthermore, "halogenated (cyclo)alkyl group" refers to an alkyl or cycloalkyl group formed by at least a portion of halogenation, and "halogenated aryl group" refers to an aryl group formed by at least a portion of halogenation.

[0103] To further enhance the reactivity of (a) resin with (b) amine compound, the electron-withdrawing group is preferably one or more groups selected from the group consisting of nitro, cyano, sulfon, and sulfonyl groups, and more preferably one or more groups selected from the group consisting of nitro, cyano, and sulfonyl groups. The same applies to the case where (a) resin has electron-withdrawing groups in the repeating unit.

[0104] When (a) resin is a resin containing an amide bond in the repeating unit and is a polyimide precursor, a polyamide-imide precursor or a polybenzoxazole precursor, (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 nitro, cyano, sulfonyl and sulfonyl groups.

[0105] (a) The resin preferably has an acidic group in at least one of the main chain, side chain, and end group 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 carboxyl group, a carboxylic anhydride group, or a sulfonic acid group. Furthermore, regarding the resin (a), from the viewpoint of inhibiting the salt formation of the amine compound (b) caused by the carboxyl group, etc., in the resin (a), or inhibiting the reaction between the resin (a) and the amine compound (b), the resin (a) is also preferably free of carboxyl groups, carboxylic anhydride groups, and sulfonic acid groups.

[0106] In this invention, from the viewpoint of improving sensitivity, the acid equivalent of (a) resin is preferably 200 g / mol or more, more preferably 400 g / mol or more. Furthermore, from the viewpoint of suppressing film thickness reduction during development, improving reactivity with (b) amine compounds, and improving sensitivity, the acid equivalent of (a) resin is preferably 500 g / mol or more, more preferably 700 g / mol or more, further preferably 1,000 g / mol or more, 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 residue after development, the acid equivalent of (a) resin is preferably 4,000 g / mol or less, more preferably 3,000 g / mol or less, and further preferably 2,500 g / mol or less.

[0107] Furthermore, in this invention, from the viewpoint of improving sensitivity, the carboxylic acid equivalent of (a) resin is preferably 200 g / mol or more, more preferably 400 g / mol or more. Additionally, from the viewpoint of suppressing film thickness reduction during development, improving reactivity with (b) amine compounds, and improving sensitivity, the carboxylic acid equivalent of (a) resin is preferably 500 g / mol or more, more preferably 700 g / mol or more, further preferably 1,000 g / mol or more, 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 residue after development, the carboxylic acid equivalent of (a) resin is preferably 4,000 g / mol or less, more preferably 3,000 g / mol or less, and further preferably 2,500 g / mol or less. Furthermore, from the viewpoint of suppressing salt formation of (b) amine compounds caused by carboxyl groups in (a) resin, or suppressing the hindrance of reaction between (a) resin and (b) amine compounds, (a) resin is also preferably free of carboxyl groups.

[0108] In this invention, from the viewpoints of suppressing film thickness reduction during development, improving reactivity with (b) amine compounds, and increasing sensitivity, it is more preferable that the acid equivalent of (a) resin is 500 g / mol or more, and the carboxylic acid equivalent of (a) resin is 500 g / mol or more, or that (a) resin does not have carboxyl groups. In the case of such a structure, (a) resin is more preferably a resin containing amide bonds in the repeating units, and is a polyimide precursor, a polyamide-imide precursor, or a polybenzoxazole precursor.

[0109] The polyimide precursor has two ammonium acid structures, two ammonium ester structures, two ammonium acid amide structures, an ammonium acid and an ammonium ester structure, an ammonium acid and an ammonium acid amide structure, or an ammonium ester and an ammonium acid amide structure in a repeating unit containing amine residues and carboxylic acid residues. Furthermore, an ammonium acid structure refers to a structure having one carboxylic acid amide bond and one carboxyl group. An ammonium ester structure refers to a structure having one carboxylic acid amide bond and one carboxylic acid ester bond. An ammonium 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 amine residues and carboxylic acid residues. The polyamide-imide precursor has an amide and an ammonium acid structure, an amide and an ammonium ester structure, or an amide and an ammonium acid amide structure in a repeating unit containing amine residues and carboxylic acid residues.

[0110] Regarding the polyimide precursor, from the viewpoint of suppressing film thickness reduction during development, improving reactivity with (b)amine compounds, and increasing sensitivity, the total percentage of the amyl ester structure (hereinafter, "esterification rate") and the total percentage of the amyl amide structure (hereinafter, "amidification rate") among the amyl acid structure, amyl ester structure, amyl amide structure, and imide closed-ring structure is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more. On the other hand, the total percentage of the amyl ester structure and the total percentage of the amyl amide structure is preferably 100 mol% or less, more preferably 99 mol% or less, further preferably 95 mol% or less, and further preferably 90 mol% or less.

[0111] The amamide ester structure of the polyimide precursor is preferably an ester structure of a monovalent organic group having 1 to 20 carbon atoms. There are no particular limitations on the monovalent organic group; examples include: aliphatic hydrocarbon groups (alkyl, alkenyl, or alkynyl, etc.), alicyclic hydrocarbon groups (cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl, etc.), aromatic hydrocarbon groups (aryl, arylalkyl, or alkylaryl, etc.), hydroxyalkyl, alkoxy, alkenyloxy, alkoxyalkyl, acyl, or acylalkyl, etc.

[0112] The monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl or acylalkyl group having 1 to 20 carbon atoms. From the viewpoint of suppressing the reduction in film thickness during development, improving the reactivity with (b)amine compounds, and improving sensitivity, the alkyl group preferably has 1 or more carbon atoms, more preferably 2 or more, and even more preferably 3 or more, and particularly preferably 4 or more. On the other hand, from the viewpoint of suppressing the reduction in film thickness during development, improving the reactivity with (b)amine compounds, and improving sensitivity, the alkyl group preferably has 20 or fewer carbon atoms, more preferably 15 or fewer carbon atoms, and even more preferably 10 or fewer carbon atoms.

[0113] There are no particular limitations on the alkyl group, and examples include: methyl, ethyl, propyl, isopropyl, butyl, 1,2-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, heptyl, octyl, nonyl, and decyl. There are also no particular limitations on the alkenyl or ynyl group, and examples include groups formed by replacing a portion of the single bonds of the alkyl group having 2 to 20 carbon atoms with unsaturated bonds.

[0114] From the viewpoint of improving reactivity with (b) amine compounds, (a) resin is preferably having electron-withdrawing groups, and (a) resin contains selected from

[0115] (a1) includes the polyimide or polyamide-imide (hereinafter referred to as "(a1) resin") that is a constituent unit represented by formula (1).

[0116] (a2) includes the polyimide precursor or polyamide-imide precursor of the constituent unit represented by formula (2) (hereinafter referred to as "(a2) resin").

[0117] (a3) includes the polyamide-imide (hereinafter referred to as "(a3) resin") that is the constituent unit represented by formula (3).

[0118] (a4) includes the polybenzoxazole (hereinafter referred to as "(a4) resin"), which is a constituent unit represented by formula (4), and

[0119] (a5) includes the polybenzoxazole precursor of the constituent unit represented by formula (5) (hereinafter referred to as "(a5) resin")

[0120] One or more resins in the group.

[0121] (a) The resin is more preferably having an electron-withdrawing group in the repeating unit, and (a) the resin comprises one or more resins selected from the group consisting of (a1) resin, (a2) resin, (a3) ​​resin, (a4) resin and (a5) resin.

[0122] From the viewpoint of improving the reactivity of (a) resin with (b) amine compound and improving sensitivity, (a) resin is more preferably (a2) resin or (a5) resin.

[0123] [Chemistry 6]

[0124]

[0125] In equation (1), L 1 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom or divalent organic group with 1 to 20 carbon atoms.

[0126] There are no particular limitations on the divalent organic group, and examples include: aliphatic hydrocarbon groups (alkylene, alkenyl, or ynylene, etc.), alicyclic hydrocarbon groups (cycloalkylene, cycloalkylalkylene, or alkylcycloalkylene, etc.), aromatic hydrocarbon groups (arylene, arylalkylene, or alkylarylene, etc.), hydroxyalkylene, alkoxyalkylene, or acylalkylene, etc. Among these, for the sake of excellent heat resistance, cycloalkylene, alkylcycloalkylene, arylene, or alkylarylene are more preferred, and cycloalkylene or arylene are particularly preferred.

[0127] There are no particular limitations on the alkylene group, and examples include: methylene, ethylene, propylene, isopropylene, butylene, 1,2-dimethylethylene, pentylene, 1-methylbutylene, 2-methylbutylene, heptylene, octylene, nonylene, and decylene.

[0128] There are no particular limitations on the cycloalkyl groups, and examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclohexadecyl, and cyclooctadecyl.

[0129] There are no particular restrictions on what constitutes an aryl group; examples include: phenylene, naphthylene, methylphenylene, ethylphenylene, methylnaphthylene, and dimethylnaphthylene.

[0130] L 1 In X 1 ~X 4 Any position in, and X 5 ~X 8 Connect at any position in the list. Indicates the bonding location. X n (n=1~8) are CR n (n=1~8). R n (n=1~8) are groups selected independently from hydrogen atoms, electron-withdrawing groups and monovalent organic groups with carbon numbers of 1 to 20.

[0131] There are no particular limitations on the monovalent organic group, and examples include: aliphatic hydrocarbon groups (alkyl, alkenyl, or alkynyl, etc.), alicyclic hydrocarbon groups (cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl, etc.), aromatic hydrocarbon groups (aryl, arylalkyl, or alkylaryl, etc.), hydroxyalkyl, alkoxy, alkenyloxy, alkoxyalkyl, acyl, or acylalkyl, etc. Among these, cycloalkyl, alkylcycloalkyl, aryl, or alkylaryl are more preferred for their excellent heat resistance, and cycloalkyl or aryl are particularly preferred.

[0132] As an alkyl group, there are no particular limitations; examples include: methyl, ethyl, propyl, isopropyl, butyl, 1,2-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, heptyl, octyl, nonyl, and decyl.

[0133] There are no particular limitations on the cycloalkyl group; examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclohexadecyl, and cyclooctadecyl.

[0134] As alkylcycloalkyl, examples include groups formed by combining the alkyl group with a cycloalkyl group.

[0135] There are no particular restrictions on the aryl group; examples include phenyl, naphthyl, methylphenyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl.

[0136] There are no particular limitations on the alkylaryl group; for example, groups formed by combining the alkyl group with an aryl group can be listed.

[0137] In L 1 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=2~3, 6~7) have electron-withdrawing groups. This is because the electron-withdrawing groups enhance the reactivity of the imide bond in formula (1) with the amine compound (b). Furthermore, in L… 1 In the case of sulfonyl or >C(CF3)2, due to L 1 It has electron-withdrawing properties, therefore even in R n (n=2~3, 6~7) lacks electron-withdrawing groups, and the reactivity of the imide bond in formula (1) with the amine compound (b) is also increased. Of course, even in the case described above, in R n (n=2~3, 6~7) may also contain electron-withdrawing groups.

[0138] [Chemistry 7]

[0139]

[0140] In equation (2), L 2 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. There are no particular restrictions on the divalent organic group with 1 to 20 carbon atoms; for example, it can be listed as L in formula (1). 1 Organogroups exemplified by divalent organic groups having 1 to 20 carbon atoms. L 2 In X 11 ~X 14 Any position in, and X 15 ~X 18 Connect at any position in the list. Indicates the bonding location.

[0141] X n (n=11~18) are CR n (n=11~18). R n (n=9~18) are groups selected independently from the group consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organogroups with 1 to 20 carbon atoms. There are no particular restrictions on the monovalent organogroups with 1 to 20 carbon atoms; for example, they can be listed as R in equation (1). n Organogroups with 1 to 20 carbon atoms (n=1 to 8) are exemplified as monovalent organogroups.

[0142] In L2 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=12~13, 16~17) have electron-withdrawing groups. This is because the electron-withdrawing groups enhance the reactivity of the amide bond in formula (2) with the amine compound (b). Furthermore, in L… 2 In the case of sulfonyl or >C(CF3)2, due to L 2 It has electron-withdrawing properties, therefore even in R n (n=12~13, 16~17) lack electron-withdrawing groups, and the reactivity of the amide bond in formula (2) with the amine compound (b) is also increased. Of course, even in the case described above, in R n (n=12~13, 16~17) may also contain electron-withdrawing groups.

[0143] [Chemistry 8]

[0144]

[0145] In equation (3), L 3 It is an amide bond. L 3 With X 19 ~X 22 Link to any position in X. n (n=19~22) are CR n (n=19~22). R n (n=19~22) are groups selected independently from the group consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organogroups with 1 to 20 carbon atoms. There are no particular restrictions on the monovalent organogroups with 1 to 20 carbon atoms; for example, they can be listed as R in equation (1). n Organogroups with 1 to 20 carbon atoms (n=1 to 8) are exemplified. Regarding the reason for increasing the reactivity of the amide bond in formula (3) with the amine compound (b), R... n One or more of the ones in (n=20~21) have electron-withdrawing groups. Indicates the bonding location.

[0146] [Chemistry 9]

[0147]

[0148] In equation (4), L 4 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. There are no particular restrictions on the divalent organic group with 1 to 20 carbon atoms; for example, it can be listed as L in formula (1). 1 Organogroups exemplified by divalent organic groups having 1 to 20 carbon atoms. L 4 In X 31 ~X35 Any position in, and X 36 ~X 40 Connect at any position in the list. 1 With X 23 ~X 26 Link any position in the string. 2 With X 27 ~X 30 Link any position in the string. 1 and 2 Indicates the bonding location.

[0149] X n (n=23~40) are CR n (n=23~40). R n (n=23~40) are groups selected independently from the group consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organogroups with 1 to 20 carbon atoms. There are no particular restrictions on the monovalent organogroups with 1 to 20 carbon atoms; for example, they can be listed as R in equation (1). n Organogroups with 1 to 20 carbon atoms (n=1 to 8) are exemplified as monovalent organogroups.

[0150] In L 4 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=33, 38) have electron-withdrawing groups. This is because the electron-withdrawing groups enhance the reactivity of the oxazole ring in formula (4) with the amine compound (b). Furthermore, in L... 4 In the case of sulfonyl or >C(CF3)2, due to L 4 It has electron-withdrawing properties, therefore even in R n (n=33, 38) lack electron-withdrawing groups, and the reactivity of the oxazole ring in formula (4) with the amine compound (b) is also increased. Of course, even in the aforementioned cases, in R n (n=33, 38) may also contain electron-withdrawing groups.

[0151] [Chemistry 10]

[0152]

[0153] In equation (5), L 5 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. There are no particular restrictions on the divalent organic group with 1 to 20 carbon atoms; for example, it can be listed as L in formula (1). 1 Organogroups exemplified by divalent organic groups having 1 to 20 carbon atoms. L5 In X 49 ~X 53 Any position in, and X 54 ~X 58 Connect at any position in the list. 3 With X 41 ~X 44 Link any position in the string. 4 With X 45 ~X 48 Link any position in the string. 3 and 4 Indicates the bonding location.

[0154] X n (n=41~58) are CR n (n=41~58). R n (n=41~58) are groups selected independently from the group consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organogroups with 1 to 20 carbon atoms. There are no particular restrictions on the monovalent organogroups with 1 to 20 carbon atoms; for example, they can be listed as R in equation (1). n Organogroups with 1 to 20 carbon atoms (n=1 to 8) are exemplified as monovalent organogroups.

[0155] In L 5 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the groups (n=51, 56) have electron-withdrawing groups. This is because the electron-withdrawing groups enhance the reactivity of the amide bond in formula (5) with the amine compound (b). Furthermore, in L... 5 In the case of sulfonyl or >C(CF3)2, due to L 5 It has electron-withdrawing properties, therefore even in R n (n=51, 56) lack electron-withdrawing groups, and the reactivity of the amide bond in formula (5) with the amine compound (b) is also increased. Of course, even in the aforementioned cases, in R n (n=51, 56) may also contain electron-withdrawing groups.

[0156] Regarding resin (a), from the viewpoint of improving reactivity with amine compound (b), it is preferable that, in the case where resin (a) has resin (a1), R n Any one or more of the groups (n=1~8) have electron-withdrawing groups.

[0157] In the case where resin (a) has resin (a2), R n Any one or more of the groups (n=11~18) have electron-withdrawing groups.

[0158] In the case where resin (a) has resin (a3), R n Any one or more of the groups (n=19~22) have electron-withdrawing groups.

[0159] In the case where resin (a) has resin (a4), R n Any one or more of the groups (n=23~40) have electron-withdrawing groups.

[0160] In the case where resin (a) has resin (a5), R n One or more of the ones in (n=41~58) have electron-withdrawing groups.

[0161] <(a) Fluorine content in the resin structure>

[0162] From the viewpoint of suppressing the reduction in film thickness during development, improving the reactivity with (b) amine compounds, and increasing sensitivity, (a) resin is preferably satisfied with the following condition (P1α). (a) resin is more preferably satisfied with the following condition (P2α).

[0163] The content of fluorine in the structure of (a) resin is less than 10,000 ppm by mass.

[0164] The content of (P2α) fluoride ions in the structure of (a) resin is less than 10,000 ppm by mass.

[0165] From the viewpoint of the effects of the invention, the content of fluorine in the structure of (a) resin is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, further preferably 0.030 ppm by mass or more, further 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 invention, the content of fluorine is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, further preferably 1,000 ppm by mass or less, further 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 content of fluorine is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, further preferably 10 ppm by mass or less, further preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.

[0166] The preferred range of the content of fluoride ions in the structure of resin (a) is also the same as the preferred range of the content of fluorine element in the structure of resin (a).

[0167] The content of fluorine in the structure of resin (a) can be 0 ppm by mass. The content of fluoride ions in the structure of resin (a) can also be 0 ppm by mass.

[0168] By making the content of fluorine in the photosensitive resin composition of resin (a) below a specific value, the content of fluorine or fluoride ions or anions containing fluorine from these resins is made below a specific value. Therefore, it is speculated that the protons in the photosensitive resin composition are locally activated through the interaction of hydrogen bonds and other components in the photosensitive resin composition. Therefore, it is believed that the effect of suppressing the reduction of film thickness during development and improving sensitivity becomes more significant by promoting local dissolution relative to the developer. In addition, since the steric hindrance of fluorine or fluoride ions is suppressed, it is also believed that the reaction between resin (a) and amine compound (b) is promoted, and the effect of improving sensitivity becomes more significant.

[0169] From the viewpoint of suppressing the reduction in film thickness during development, improving reactivity with (b)amine compounds, and increasing sensitivity, the photosensitive resin composition of the present invention preferably satisfies at least one of the conditions described in (P1α) and the conditions described below in (1α). More preferably, the photosensitive resin composition of the present invention satisfies at least one of the conditions described in (P2α) and the conditions described below in (2α).

[0170] (1α) The content of fluorine in all solid components of the photosensitive resin composition is less than 1,000 ppm by mass.

[0171] (2α) The content of fluoride ions in all solid components of the photosensitive resin composition is less than 1,000 ppm by mass.

[0172] From the viewpoint of the effects of the invention, the content of fluorine in all solid components 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 invention, the content of 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 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.

[0173] The preferred range of the content of fluoride ions in all solid components of the photosensitive resin composition is also the same as the preferred range of the content of fluorine element in all solid components of the photosensitive resin composition.

[0174] The content of fluorine in all solid components of the photosensitive resin composition may be 0 ppm by mass. The content of fluoride ions in all solid components of the photosensitive resin composition may also be 0 ppm by mass. When the content of fluorine and / or the content of fluoride ions in all solid components of the photosensitive resin composition exceeds 0 ppm by mass, the photosensitive resin composition of the present invention preferably has (a) a resin, (b) an amine compound, or (c) a photoacid generator having fluorine atoms or fluoride ions in its structure, or further contains components containing fluorine and / or components containing fluoride ions.

[0175] By setting the content of compounds containing fluorine atoms in the structure or components containing fluorine elements in the photosensitive resin composition to a specific value or below, the content of fluorine elements or fluoride ions or anions containing fluorine elements derived from these components is also set to a specific value or below. As a result, it is speculated that protons in the photosensitive resin composition are locally activated through the interactions of hydrogen bonds and the like among the components in the photosensitive resin composition. Therefore, it is believed that the effect of suppressing the reduction in film thickness during development and improving sensitivity becomes more significant through the local dissolution-promoting effect relative to the developer. In addition, since the steric hindrance of fluorine elements or fluoride ions is suppressed, it is also believed that the reaction between (a) resin and (b) amine compound is promoted, and the effect of improving sensitivity becomes more significant.

[0176] To further improve the heat resistance of the cured product obtained by curing the photosensitive resin composition, (a) the resin content is preferably 3% by mass or more relative to 100% by mass of the photosensitive resin composition. Furthermore, to produce a photosensitive resin composition with higher sensitivity, (a) the resin content is preferably 30% by mass or less relative to 100% by mass of the photosensitive resin composition.

[0177] <(b) Amine compounds>

[0178] The photosensitive resin composition of the embodiments of the present invention contains a (b)amine compound. Furthermore, the (b)amine compound is a primary or secondary amine. The (b)amine compound is preferably one or more compounds selected from the group consisting of monoamine compounds, diamine compounds, triamine compounds, and tetraamine compounds. From the viewpoint of suppressing residue after development, the (b)amine compound is more preferably a monoamine compound. From the viewpoint of improving sensitivity, the (b)amine compound is more preferably one or more compounds selected from the group consisting of diamine compounds, triamine compounds, and tetraamine compounds. Furthermore, the (b)amine compound may also be a polyamine compound having five or more amino groups in its 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.

[0179] The photosensitive resin composition of the present invention preferably contains a monoamine compound as a primary or secondary amine. Examples of monoamine compounds include: R 59 The compound represented by NH2, R 60 Compounds represented by 2NH, cyclic compounds such as pyrrolidine, piperidine, indole, or pyrrole, or heteroaromatic compounds.

[0180] Here, R 59 and R 60 Each is an independent monovalent organic group having 1 to 20 carbon atoms. There are no particular restrictions on what constitutes a monovalent organic group; examples include: aliphatic hydrocarbon groups (alkyl, alkenyl, or alkynyl, etc.), alicyclic hydrocarbon groups (cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl, etc.), aromatic hydrocarbon groups (aryl, arylalkyl, or alkylaryl, etc.), hydroxyalkyl, alkoxy, alkenyloxy, alkoxyalkyl, acyl, or acylalkyl, etc.

[0181] The monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl or acylalkyl group having 1 to 20 carbon atoms. Among these, for the sake of low steric hindrance and improved reactivity with resin (a), alkyl, alkenyl, alkynyl, cycloalkylalkyl, arylalkyl, hydroxyalkyl, alkoxy, alkenyloxy, alkoxyalkyl, acyl or acylalkyl groups are more preferred, and alkyl groups are particularly preferred.

[0182] There are no particular limitations on the alkyl group, and examples include: methyl, ethyl, propyl, isopropyl, butyl, 1,2-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, heptyl, octyl, nonyl, and decyl. There are also no particular limitations on the alkenyl or ynyl group, and examples include groups formed by replacing a portion of the single bonds of the alkyl group having 2 to 20 carbon atoms with unsaturated bonds.

[0183] There are no particular limitations on the cycloalkyl group; examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclohexadecyl, and cyclooctadecyl. Examples of cycloalkyl groups formed by combining the aforementioned cycloalkyl groups with alkyl groups can also be included.

[0184] There are no particular limitations on whether the aryl or alkylaryl group is used; examples include phenyl, naphthyl, methylphenyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl. There are also no particular limitations on whether the aryl alkyl group is used; examples include groups formed by combining the aryl group with an alkyl group.

[0185] There are no particular limitations on the hydroxyalkyl group; examples include groups formed by replacing a portion of the hydrogen atom of the alkyl group having 1 to 20 carbon atoms with a hydroxyl group. There are no particular limitations on the alkoxy or alkenyloxy group; examples include groups formed by bonding an oxygen atom to the alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. There are no particular limitations on the alkoxyalkyl group; examples include groups formed by replacing a portion of the single bond of the alkyl group having 1 to 20 carbon atoms with an ether bond.

[0186] There are no particular limitations on the acyl or acylalkyl group; for example, groups formed by replacing one of the two hydrogen atoms on the same carbon atom of the alkyl group having 1 to 20 carbon atoms with a double bond to an oxygen atom are listed.

[0187] In cyclic or heteroaromatic compounds, a portion of the hydrogen atom on the carbon atom can be substituted by hydroxyl, carboxyl, aldehyde, sulfonyl, or other groups. In cyclic or heteroaromatic compounds containing -CH2- in the molecule, a portion of the -CH2- group can be substituted by ether, ester, carbonyl, sulfonyl, or other groups.

[0188] By using (b) an amine compound that is either a primary or secondary amine, steric hindrance is minimized, resulting in high reactivity with (a) resin. From the viewpoint of further enhancing the aforementioned effect, it is more preferable that (b) an amine compound is a primary amine.

[0189] For the purpose of further improving reactivity with resin (a), the amine compound in (b) is preferably an aliphatic amine, alicyclic amine, or cyclic amine in which electron pairs readily exist on the nitrogen atom of the amine, and more preferably an aliphatic amine. Furthermore, an aliphatic amine is a compound in which the aliphatic hydrocarbon group is bonded to the nitrogen atom of the amino group. An alicyclic amine is a compound in which the alicyclic hydrocarbon group is bonded to the nitrogen atom of the amino group. A cyclic amine is a compound in which the nitrogen atom of the amino group is a ring member atom of a cyclic structure rather than a heteroaromatic ring member atom. Additionally, from the viewpoint of controlling reactivity with resin (a) or improving the storage stability of the photosensitive resin composition, the amine compound in (b) is also preferably an aromatic amine or a heteroaromatic amine. An aromatic amine is a compound in which the aromatic hydrocarbon group is bonded to the nitrogen atom of the amino group. A heteroaromatic amine is a compound in which the nitrogen atom of the amino group is a heteroaromatic ring member atom.

[0190] Regarding the (b) amine compound, the higher the basicity, the greater the reactivity with the (a) resin. Therefore, its basic dissociation constant (pKb) is preferably 6 or less, more preferably 4 or less. Furthermore, there is no particular limitation on the lower limit of the pKb of the (b) amine compound, but it is preferably -14 or more.

[0191] There are no particular limitations on specific examples of preferred (b) amine compounds. Examples of primary amines 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, heptadecanylamine, octadecylamine, amino-methanol, amino-ethanol, and 3-amino-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-dodecylol, 13-Amino-1-tridecylol, 14-Amino-1-tetradecylol, 15-Amino-1-pentadecanol, 16-Amino-1-hexadecylol, 17-Amino-1-heptadecylol, 18-Amino-1-octadecylol, benzylamine, aniline, etc.

[0192] As aliphatic amines, there are no particular limitations, but examples 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, heptadecanylamine, octadecylamine, amino-methanol, amino-ethanol, 3-amino-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-dodecylol, 13-Amino-1-tridecylol, 14-Amino-1-tetradecylol, 15-Amino-1-pentadecanol, 16-Amino-1-hexadecylol, 17-Amino-1-heptadecylol, 18-Amino-1-octadecylol, etc.

[0193] As monoamine compounds with a pKb of 6 or less, there are no particular limitations, but examples 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, heptadecanylamine, octadecylamine, amino-methanol, amino-ethanol, and 3-amino-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-dodecylol, 13-Amino-1-tridecylol, 14-Amino-1-tetradecylol, 15-Amino-1-pentadecanol, 16-Amino-1-hexadecylol, 17-Amino-1-heptadecylol, 18-Amino-1-octadecylol, etc.

[0194] In addition to improving the heat resistance of the cured product obtained by curing the photosensitive resin composition, in order to reduce the amount of (b)amine compound remaining in the unexposed portion and achieve a low amount of developing film reduction, it is preferable to remove the (b)amine compound by heating during or after the reaction with (a) resin. Furthermore, to prevent deterioration of the cured product caused by heating at high temperatures, it is preferable to remove the compound at a moderate temperature. From these perspectives, the boiling point of the (b)amine compound at 1 atmosphere is preferably 300°C or less, more preferably 250°C or less, and even more preferably 200°C or less. On the other hand, during the period up to the step of reacting with (a) resin, in order to retain the (b)amine compound in the photosensitive resin composition, the boiling point of the (b)amine compound at 1 atmosphere is preferably 100°C or more, more preferably 130°C or more.

[0195] From the viewpoint of controlling the reactivity with (a) resin or improving the storage stability of the photosensitive resin composition, the (b) amine compound is preferably an amine salt. Furthermore, from the viewpoint of improving the reactivity with (a) resin and the (b) amine compound and improving sensitivity, the amine salt is preferably a compound comprising a cationic species having a primary amine structure or a secondary amine structure, and an anionic species.

[0196] The cationic species in the amine salt preferably comprises a structure derived from one or more of the group consisting of monoamine compounds, diamine compounds, triamine compounds, and tetraamine compounds. Furthermore, the cationic species in the amine salt is also preferably derived from a structure derived from a polyamine compound having five or more amino groups in its molecule. The cationic species in the amine salt is preferably composed of the aforementioned amine compounds. Examples or preferred formulations relating to the aforementioned amine compounds are the same as described above.

[0197] The anions in the amine salt are preferably selected from one or more of the group consisting of sulfonate ions, formate ions, acetate ions, oxalate ions, phenoxy ions, sulfate ions, sulfite ions, nitrate ions, nitrite ions, phosphate ions, phosphite ions, hypophosphite ions, fluoride ions, chloride ions, bromide ions, and iodide ions.

[0198] The sulfonate ion is preferably a monovalent organic group having 1 to 20 carbon atoms. There are no particular limitations on the monovalent organic group, and examples include: aliphatic hydrocarbon groups (alkyl, alkenyl, or alkynyl, etc.), alicyclic hydrocarbon groups (cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl, etc.), aromatic hydrocarbon groups (aryl, arylalkyl, or alkylaryl, etc.), hydroxyalkyl, alkoxy, alkenyloxy, alkoxyalkyl, acyl, or acylalkyl, etc.

[0199] The monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl or acylalkyl group having 1 to 20 carbon atoms.

[0200] In this invention, in order to produce a high-sensitivity photosensitive resin composition, the content of the (b)amine compound is 35 parts by mass or more relative to 100 parts by mass of (a) resin in the photosensitive resin composition. Furthermore, in this invention, the content of the monoamine compound is preferably 35 parts by mass or more relative to 100 parts by mass of (a) resin in the photosensitive resin composition. In this invention, the content of the (b)amine compound is preferably 50 parts by mass or more relative to 100 parts by mass of (a) resin, more preferably 80 parts by mass or more. On the other hand, in order to reduce the residual amount of (b)amine compound in the unexposed portion and suppress the reduction in film thickness during development, and in order to reduce the residual amount of (b)amine compound in the hardened film and improve heat resistance, the content of the (b)amine compound is preferably 1000 parts by mass or less relative to 100 parts by mass of (a) resin in the photosensitive resin composition, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less.

[0201] <(c) Photoacid generator>

[0202] The photosensitive resin composition of the embodiments of the present invention contains (c) a photoacid generating agent. A photoacid generating agent is a compound that has the function of generating acid upon exposure. (c) The photoacid generating agent may be a known photoacid generating agent without impairing the effects of the present invention.

[0203] As photoacid generators (c), examples include onium salt-type ionic photoacid generators and nonionic photoacid generators. An onium salt is a compound that generates an acid by coordination bonding between a compound having electron pairs that do not participate in chemical bonding and other cationic compounds. In ionic photoacid generators, the cation site of the onium salt determines the photochemical properties (molar absorptivity, absorption wavelength, quantum yield), while the anionic site determines the strength of the generated acid. On the other hand, nonionic photoacid generators are photoacid generators where the light-absorbing site is bonded to the acid via an ester bond.

[0204] As an ionic compound, it is preferably an ionic compound that does not contain heavy metals or halide ions, and more preferably a triorganosulfonate salt compound. Specific examples of triorganosulfonate compounds include: triphenylsulfonate methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, perfluoro-1-butanolsulfonate (“SP-056”, trade name, manufactured by ADEKA); the sulfonates of dimethyl-1-naphthylsulfonate; the sulfonates of dimethyl(4-hydroxy-1-naphthyl)sulfonate; the sulfonates of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonate; the sulfonates of diphenylsulfonate, etc.

[0205] As nonionic photoacid generators, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, sulfonylimide compounds, phosphate ester compounds, sulfone benzotriazole compounds, etc., can be used.

[0206] Specific examples of diazomethane compounds include bis(4-methylphenylsulfonyl)diazomethane (“WPAG-199”, trade name, manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.) etc.

[0207] Specific examples of sulfone compounds include β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred sulfone compounds include 2-(p-toluenesulfonyl)acetophenone and bis(phenylsulfonyl)methane.

[0208] Specific examples of sulfonate compounds include alkyl sulfonates, haloalkyl sulfonates, aryl sulfonates, and imino sulfonates. Preferred examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methyl sulfonate), nitrobenzyl-9,10-diethoxyanthrayl-2-sulfonate, and 2,6-(dinitrobenzyl)phenyl sulfonate.

[0209] Specific examples of carboxylic acid ester compounds include, for example, 2-nitrobenzyl carboxylic acid ester.

[0210] (c) The photoacid generating agent preferably contains a nonionic photoacid generating agent. By having a nonionic photoacid generating agent in (c), a photosensitive resin composition with higher sensitivity can be prepared.

[0211] (c) The photoacid generator is more preferably a photoacid generator containing an acid dissociation constant (pKa) in the range of -14 to 2, which includes an acidic group generated by light. Thus, the acidic group generated by light can act as an acid and effectively participate in the reaction between (a) the resin and (b) the amine compound.

[0212] Specific examples of photoacid generators whose acid dissociation constant (pKa) for acidic groups generated by light is in the range of -14 to 2 include photoacid generators such as trifluoromethanesulfonic acid (pKa=-14), nonafluorobutyric acid (pKa=-3.57), p-toluenesulfonic acid (pKa=-2.8), and methanesulfonic acid (pKa=-2.6).

[0213] (c) The photoacid generator is preferably 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 acid group generated by light is a sulfonate group, thus having a high pKa and being able to produce a photosensitive resin composition with higher sensitivity.

[0214] Oxime sulfonate compounds can be represented by the following structures.

[0215] [Chemistry 11]

[0216]

[0217] R 61 It is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of monovalent organic groups having 1 to 12 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, trifluoromethanesulfonate, nonafluorobutyl, perfluorooctyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-yl)methyl, benzyl, phenyl, toluenesulfonyl, naphthyl, etc.

[0218] R 62 and R 63 It is a monovalent organogroup with 1 to 30 carbon atoms. R 62 and R 64 They can be the same or different. Specific examples of monovalent organic groups with 1 to 30 carbon atoms include: cyano, trifluoromethyl, hexafluoropropyl, pentafluorobutyl, dodecylfluorohexyl, phenyl, 4-methoxyphenyl, 2-fluorenyl, 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl, etc.

[0219] R 64 It is a monovalent organogroup with 3 to 30 carbon atoms. Specific examples of monovalent organogroups with 3 to 30 carbon atoms can be listed below.

[0220] [Chemistry 12]

[0221]

[0222] Indicates the bonding location.

[0223] Specific examples of oxime sulfonates include: Irgacure (registered trademark) PAG-103 (phenylacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (phenylacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (phenylacetonitrile, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylidene), PAG-203 (all of which are manufactured by BASF Corporation of Japan), PAI-101 ((Z)-4-methoxy-N-(toluenesulfonyloxy)imine benzyl cyanide, manufactured by Midori Kagaku Corporation), etc.

[0224] Imide sulfonate compounds can be represented by the following structures.

[0225] [Chemistry 13]

[0226]

[0227] R 65 It is a monovalent organogroup having 1 to 12 carbon atoms. Specific examples of monovalent organogroups having 1 to 12 carbon atoms can be listed as R. 61 The specific examples listed are the basic ones.

[0228] R 66 and R 67 It is a monovalent organogroup with 1 to 30 carbon atoms. R 66 and R 67 They can be the same or different. Specific examples of monovalent organic groups with 1 to 30 carbon atoms can be listed as R... 62 and R 63 The specific examples listed are the basic ones.

[0229] R 68 It is a monovalent organogroup with 3 to 30 carbon atoms. Specific examples of divalent organogroups with 3 to 30 carbon atoms can be listed below.

[0230] [Chemistry 14]

[0231]

[0232] R 69 It is a monovalent organogroup with 1 to 12 carbon atoms. t represents an integer from 0 to 2. Specific examples of monovalent organogroups with 1 to 12 carbon atoms include: methyl, ethyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, 1-(hex-1-en-1-yl)yl, 1-(4-butoxyphenethyl)yl, etc. Indicates the bonding location.

[0233] Examples of imide sulfonate compounds include: N-hydroxynaphthalenedicarboximide trifluoromethanesulfonate, "ADEKA ARKLS" (registered trademark), SP-606 (4-butyl-N-hydroxynaphthalenedicarboximide trifluoromethanesulfonate, manufactured by ADEKA), NA-101 (N-hydroxynaphthalenedicarboximide-p-toluenesulfonate), NA-106 (N-hydroxynaphthalenedicarboximide camphorsulfonate, all manufactured by Midori Kagaku), etc.

[0234] In this invention, in order to produce a photosensitive resin composition with higher sensitivity, the content of (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, relative to 100 parts by mass of (a) resin in the photosensitive resin composition. On the other hand, in order to reduce the residual amount of (c) photoacid generator in the hardened film and further improve heat resistance, the content of (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, relative to 100 parts by mass of (a) resin in the photosensitive resin composition.

[0235] The photosensitive resin composition of the embodiments of the present invention preferably also contains a solvent. By containing a solvent, a film of the composition can be formed on a substrate with a desired film thickness, and the effect of improving the film thickness uniformity of the coating becomes more significant. From the viewpoint of the solubility of various resins and various additives, the solvent is preferably a solvent containing a carbonyl group, a solvent containing an ester bond, a solvent containing at least three ether bonds, or a solvent containing an alcoholic hydroxyl group. From the viewpoint of improving the film thickness uniformity of the coating, the solvent is preferably a compound with 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 thermosetting, a compound with 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 according to the coating method, etc. For example, in the case of forming a coating by spin coating, it is generally set to 50% to 95% by mass of the total photosensitive composition.

[0236] The carbonyl group is preferably an alkyl carbonyl group, a dialkyl carbonyl group, or a formyl group. The ester bond is preferably a carboxylic acid ester bond, a carbonate bond, or a formate 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 bond is more preferably a cyclic carbonate bond.

[0237] Examples of solvents containing carbonyl groups include: 2-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, or cycloheptanone.

[0238] From the viewpoint of suppressing the reaction hindrance of the acid generated from the photoacid generator (c), it is suitable to use solvents having carbonyl groups, solvents having ester bonds, solvents having at least three ether bonds, or solvents having alcoholic hydroxyl groups. Furthermore, from the viewpoint of suppressing the reaction hindrance of the acid generated from the photoacid generator (c), solvents having carbonyl groups, solvents having ester bonds, solvents having at least three ether bonds, and solvents having alcoholic hydroxyl groups are preferably free of amide groups, imide groups, urea bonds, and urethane bonds.

[0239] Examples of solvents containing ester bonds 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, or ε-butyrolactone.

[0240] In the photosensitive composition of the present invention, from the viewpoint of suppressing the reaction hindrance of the acid generated by (c) photoacid generator and improving sensitivity, the total content of the solvent having carbonyl groups, the solvent having ester bonds, the solvent having at least three ether bonds, and the solvent having alcoholic hydroxyl groups is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, further preferably 70% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0241] In the photosensitive composition of the present invention, from the viewpoint of suppressing the reaction hindrance of the acid generated by (c) photoacid generator and improving sensitivity, the total content ratio of the solvent having carbonyl groups and the solvent having ester bonds in the solvent is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, further preferably 70% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0242] In addition to the aforementioned components, the photosensitive resin composition of embodiments of the present invention may also contain other additives. Examples of such additives include: solubility promoters, sensitizers, silane coupling agents, surfactants, etc.

[0243] <Hardened material>

[0244] The cured product of the embodiments of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. Examples of curing conditions include heat treatment at 150°C to 350°C. This heat treatment allows for a thermal crosslinking reaction, improving heat resistance and chemical resistance. Preferred conditions for the heat treatment will be described later.

[0245] To further improve the heat resistance of the cured material, the content of the (b)amine compound in the cured material 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 material. On the other hand, the content of the (b)amine compound in the cured material 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 material.

[0246] <Pattern Manufacturing Method>

[0247] A method for manufacturing a pattern using the photosensitive resin composition according to embodiments of the present invention includes:

[0248] The process of coating the photosensitive resin composition of the present invention onto a substrate (hereinafter, "(a-1) process")

[0249] The process of exposing the coated material to a light-blocking mask (hereinafter, "(b-1) process")

[0250] The process of heating the coating material during or after exposure of the photomask (hereinafter, "(b-2) process")

[0251] The process of developing the heated coating (hereinafter, "(c-1) process"), and

[0252] The process of heating the developed coating (hereinafter, "(d-1) process").

[0253] The (a-1) step is a step of coating a photosensitive resin composition onto a substrate. The substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafers, ceramic stacked substrates, metal-plated substrates, sapphire, and gallium arsenide.

[0254] The method of coating the photosensitive resin composition onto the substrate can be a known method. Examples of apparatus used for coating include: spin coating, dip coating, curtain flow coating, spray coating, or slot coating, etc., for whole-surface coating, or printing apparatus such as screen printing, roller coating, microgravure coating, or inkjet printing.

[0255] After the photosensitive resin composition is coated onto the substrate, drying may be performed to remove solvents, etc. Drying is carried out using a vacuum drying apparatus or a heating device such as a hot plate or oven. When using a heating device, it is preferable to perform the drying process for 30 seconds to 30 minutes within a temperature range of 50°C to 150°C. The film thickness of the coated material (after drying) is preferably 0.1 μm or more and 100 μm or less.

[0256] Step (b-1) involves exposing the coated material to a photomask. The photomask, having the desired pattern, is used to expose the coated material. The wavelength of the electromagnetic wave used in step (b-1) is not particularly limited; examples include gamma rays (436 nm), h-rays (405 nm), or i-rays (365 nm), which have wavelengths between 300 nm and 450 nm. Preferably, the electromagnetic wave has a wavelength of 365 nm.

[0257] 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. Additionally, the wavelength of the illumination light can be adjusted using beam-splitting filters such as long-wavelength cutoff filters, short-wavelength cutoff filters, and bandpass filters, as needed.

[0258] Step (b-2) involves heating the coated material during or after exposure using a photomask. In the exposed section, the acid generated by the photoacid generator (c) acts as a catalyst, promoting the reaction between the resin (a) and the amine compound (b) through heating, and increasing the solubility contrast relative to the developer in both the unexposed and exposed sections. Heating can be performed using an oven, hot plate, infrared radiation, flash annealing apparatus, laser annealing apparatus, etc. For increasing the reactivity of the resin (a) and the amine compound (b), a heating temperature of 80°C or higher is preferred. More preferably, 100°C or higher, and even more preferably, 130°C or higher. From the viewpoint of preventing thermal crosslinking of the resin (a) and increasing the solubility contrast relative to the developer in both the unexposed and exposed sections, a temperature of 250°C or lower is preferred. 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.

[0259] Step (c-1) is a process of developing the heated coated material. To form a pattern of the photosensitive resin composition, the exposed areas are removed using a developing solution after exposure. The developing solution used is not particularly limited; organic solvents or alkaline aqueous solutions can be used. As for the organic solvent, there are no particular limitations; 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, ketones such as cyclopentanone (CP), cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, or organic solvents combining several of these can be used alone.

[0260] A typical alkaline aqueous solution is an aqueous solution containing dissolved alkaline compounds. Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate. Additionally, depending on the situation, polar solvents such as N-methyl-2-pyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone (GBL), dimethacrylamide, and α-acetyl-γ-butyrolactone, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone (CP), cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, or compounds combining several of these can be added to these alkaline aqueous solutions.

[0261] After development, rinsing is preferably performed using an organic solvent or water. When using an organic solvent, in addition to the developer, examples include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When using water, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate can also be added to the water for rinsing.

[0262] Step (d-1) involves heating the developed coating. After development, a temperature of 150°C to 350°C is applied to induce a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment can be achieved by selecting a temperature and gradually increasing it, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, heat treatments at 130°C and 200°C for 30 minutes each can be employed.

[0263] As the lower limit of the heating temperature in this invention, in order to improve the degree of thermal crosslinking reaction and to remove (b)amine compounds, it is preferably 200°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher. Furthermore, as the upper limit of the heating temperature, in order to prevent the deterioration of the hardened material, it is preferably 350°C or lower, more preferably 300°C or lower.

[0264] There are no particular limitations on the heating environment; it can be carried out under atmospheric conditions or inert environments such as nitrogen or argon. To prevent degradation, it is preferable to carry out the process in an inert environment.

[0265] The cured material obtained by the pattern manufacturing method according to the embodiments of the present invention is a cured material mainly composed of polyimide, polyamide-imide, or polybenzoxazole, and therefore has excellent heat resistance.

[0266] <Electronic Components>

[0267] The cured product obtained by curing the photosensitive resin composition according to embodiments of the present invention can be used as an insulating film or protective film constituting electronic components. Here, examples of electronic components include: active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memory, as well as passive components such as resistors, capacitors, and inductors. In addition, electronic components using semiconductors are also referred to as semiconductor devices or semiconductor packages.

[0268] <Organic Electroluminescence (EL) Display Devices>

[0269] The cured product obtained by curing the photosensitive resin composition according to embodiments of the present invention can be used as an insulating film or protective film constituting a display device. The cured product of the photosensitive resin composition of the present invention is particularly suitable as a planarization layer or insulating layer constituting an organic EL display device. Specifically, an organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and the planarization layer and / or the insulating layer comprising the cured film, is preferred. Taking an active matrix type display device as an example, a TFT and wiring located on the side of the TFT and connected to the TFT are provided on a substrate such as glass or a resin film. A planarization layer is provided thereon in a manner that covers unevenness, and then a display element is disposed on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer.

[0270] The cured product obtained by curing the photosensitive resin composition according to embodiments of the present invention is preferably used as a planarization layer in an organic EL display device due to its excellent planarization properties and pattern dimensional stability. In particular, in recent years, the flexibility of organic EL display devices has become mainstream, and organic EL display devices with a substrate having the aforementioned driving circuit containing a resin film can also be used.

[0271] Example

[0272] The following examples and comparative examples are provided to further illustrate the present invention, but the invention is not limited to these scopes. Furthermore, compounds used in this study that are abbreviated are shown below with their names.

[0273] <Carboxylic acid derivatives>

[0274] BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride

[0275] NBPDA: 6-Nitro-3,3',4,4'-Biphenyltetracarboxylic dianhydride

[0276] DSDA: 3,3',4,4'-Diphenylsulfone tetracarboxylic dianhydride

[0277] BP-HBT: A mixture of dicarboxylic acid derivatives obtained by reacting 4,4'-biphenyldicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole.

[0278] BPDCC: 4,4'-Biphenyldicarboxylic acid dichloride

[0279] TMAC: Trimethicone Chloride

[0280] <Amine Derivatives>

[0281] DABP: 4,4'-Diamino-biphenyl

[0282] DADHBP: 3,3'-Diamino-4,4'-Dihydroxybiphenyl

[0283] <Esterifying Agent>

[0284] DFA: N,N-dimethylformamide dimethyl acetal

[0285] <(b) Amine compounds>

[0286] HA: Hexylamine (primary aliphatic amine, boiling point 133℃, pKb 3.4)

[0287] DBA: Dibutylamine (secondary aliphatic amine, boiling point 159℃, pKb 2.7)

[0288] TBA: Tributylamine (a tertiary aliphatic amine, boiling point 216℃, pKb 4.0)

[0289] BEA: Benzylamine (a primary aromatic amine, boiling point 185℃, pKb 4.7)

[0290] AN: Aniline (a primary aromatic amine, boiling point 184℃, pKb 9.4)

[0291] BA: Butylamine (primary aliphatic amine, boiling point 78℃, pKb 3.2)

[0292] PA: Pentylamine (primary aliphatic amine, boiling point 104℃, pKb 3.8)

[0293] OA: Octylamine (primary aliphatic amine, boiling point 176℃, pKb 3.3)

[0294] AH: 6-Amino-1-hexanol (primary aliphatic amine, boiling point 225℃, pKb -1.2)

[0295] AD: 10-Amino-1-decanol (primary aliphatic amine, boiling point 269℃, pKb -1.2)

[0296] ADD: 12-Amino-1-dodecyl alcohol (primary aliphatic amine, boiling point 304℃, pKb -1.2)

[0297] HMDA: Hexamethylenediamine

[0298] DAPA: 3,3'-Diaminodipropylamine

[0299] HA-PTS: Hexylammonium p-toluenesulfonate (an amine salt containing a cationic species with a primary aliphatic amine structure and an anionic species as a sulfonate ion).

[0300] AN-PTS: Phenylamine p-toluenesulfonate (an amine salt containing a cationic species with a primary aromatic amine structure and an anionic species as a sulfonate ion).

[0301] <(c) Photoacid generator>

[0302] PAG-103: "Irgacure" (registered trademark) PAG-103 (phenylacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thionyl, maximum absorption wavelength: 405 nm, molecular weight 348, manufactured by BASF Corporation, Japan)

[0303] <Solvent>

[0304] CP: Cyclopentanone

[0305] <Compounds containing fluorine>

[0306] Fc-1: 2,2-bis(4-hydroxyphenyl)hexafluoropropane

[0307] FI-1: (decyltriethyl)ammonium fluoride.

[0308] (1) Weight average molecular weight

[0309] The molecular weight (Mw) of polystyrene was determined using a gel permeation chromatography (GPC) analyzer under the following conditions.

[0310] Measuring apparatus: Waters 2695 (manufactured by Waters Corporation)

[0311] Column temperature: 50℃

[0312] Flow rate: 0.4 mL / min

[0313] Detector: 2489 Ultraviolet-Visible Detector (UV / VisDetector) (measurement wavelength 260 nm)

[0314] Developing solvent: NMP (containing 0.21% by weight lithium chloride and 0.48% by weight phosphoric acid)

[0315] Guard column: TOSOH TSK guard column (manufactured by TOSOH)

[0316] Tubing: TOSOH TSK-GEL a-2500

[0317] TOSOH TSK-GEL a-4000 series (all manufactured by TOSOH).

[0318] (2) Phenolic equivalent and carboxylic acid equivalent

[0319] An automatic potentiometric titration apparatus (AT-510; manufactured by Kyoto Electronics Industry Co., Ltd.) was used, with a 0.1 mol / L sodium hydroxide / ethanol solution as the titrant and xylene / N,N-dimethylformamide = 1 / 1 (mass ratio) as the titrant solvent. Based on Japanese Industrial Standards (JIS) K2501 (2003), the phenol value (unit: mgKOH / g) or carboxylic acid value (unit: mgKOH / g) was determined and calculated using potentiometric titration. The phenol equivalent (unit: g / mol) or carboxylic acid equivalent (unit: g / mol) was then calculated based on the determined phenol or carboxylic acid value.

[0320] In cases where the composition contains multiple resins with phenolic hydroxyl or carboxyl groups, the components that can be separated from the composition are removed by methods such as centrifugation, liquid-liquid extraction, and column chromatography. Subsequently, the resins are separated by GPC separation. Then, based on the method for determining the phenolic equivalent or carboxylic acid equivalent, the carboxylic acid equivalent (in g / mol) is calculated.

[0321] (3) Imidine ring-closing rate and benzoxazole ring-closing rate of resin

[0322] Regarding the imide ring-closure rate, resin solutions were prepared by dissolving each resin in GBL at a concentration of 35% by mass. The obtained resin solutions were coated onto silicon wafers using a spin coater (1H-DX; Mikasa Corporation), and then baked at 120°C for 180 seconds to produce resin films with a thickness of 4 μm to 5 μm. The silicon wafers with the resin films were then divided in two. One wafer was heated in a clean oven (CLH-21CD-S; Koyo ThermoSystem Corporation) at 140°C for 30 minutes under a nitrogen atmosphere with an oxygen concentration of less than 20 ppm by mass, followed by further heating to 320°C for 60 minutes to completely close the imide ring (the heated resin film). The other wafer was used directly without heat treatment (the unheated resin film). The transmitted infrared absorption spectra of the resin films before and after heating were measured using an infrared spectrophotometer (FT-720; Horiba Corporation). The absorption peak (1,780 cm⁻¹) caused by the polyimide structure was confirmed. -1 Nearby, 1,377 cm -1 After considering the presence of (nearby) areas, the initial 1,377 cm² was calculated. -1 Peak intensity (X) nearby, 1,377 cm² after heating -1 The peak intensity (Y) near the target. The imide ring-closure ratio in the resin film before heating is calculated using the following formula.

[0323] The cyclic closure rate of imide [%] = (X / Y) × 100.

[0324] Regarding the benzoxazole ring-closure rate, a resin film with a thickness of 4 μm to 5 μm was prepared using the same method as described above. The prepared silicon wafer with the resin film was divided into two halves. One half was heated at 320°C for 30 minutes using a buzzer hot plate (HPD-3000BZN; manufactured by ASONE) to completely close the benzoxazole ring (the heated resin film). The other half was used directly without heating (the unheated resin film). The transmitted infrared absorption spectra of the resin films before and after heating were measured using an infrared spectrophotometer (FT-720; manufactured by Horiba Corporation). The absorption peak of the benzoxazole structure caused by polybenzoxazole was confirmed (1,570 cm⁻¹). -1 After considering the presence of the peak value caused by the stretching vibration of C=C (C=N) in the vicinity, the 1,570 cm⁻¹ before heating was calculated. -1 Peak intensity (P) near the site, 1,570 cm² after heating -1 The peak intensity (Q) near the target. The benzoxazole ring-closure rate in the resin film before heating is calculated using the following formula.

[0325] The circumference closure rate of benzoxazole [%] = (P / Q) × 100.

[0326] (4) The molar ratio of polyimide units, etc.

[0327] Each resin was separated and used after being processed by GPC separation. Furthermore, regarding the resins in the composition, the composition was extracted with dichloromethane, and after ultracentrifugation, the resins were separated from the dichloromethane-insoluble residue by GPC separation before use. Each resin was analyzed using proton nuclear magnetic resonance spectrometry, infrared spectroscopy, pyrolysis gas chromatography-mass spectrometry, and reaction pyrolysis gas chromatography-mass spectrometry. Based on the obtained measurement results, the structures of each unit (imide structure), polyimide precursor unit (amic acid structure and amic acid ester structure), polybenzoxazole unit (benzoxazole structure), polybenzoxazole precursor unit (hydroxyamide structure), and polyamide-imide unit (imide structure and amide structure), as well as the structures of the comonomers constituting these units, were determined. Next, each comonomer was prepared as a standard sample, and the inherent peak values ​​of each comonomer were confirmed by proton nuclear magnetic resonance spectrometry. Subsequently, based on the area ratio of the peak values ​​of the proton nuclear magnetic resonance spectra of each resin, the molar ratio of each unit in the resin to the comonomers that constitute them was calculated.

[0328] (5) Content of specific elements in the resin or composition

[0329] The fluorine content in the resin or composition was determined by combustion ion chromatography under the following conditions. The resins in the resin and composition were separated by GPC separation, or by dichloromethane extraction, ultracentrifugation, and GPC separation before use. The resin or composition was combusted and decomposed in the combustion tube of the analytical apparatus, and the resulting gas was absorbed by the absorbent. A portion of the absorbent was then analyzed by ion chromatography. Furthermore, the content of all solid components in the composition was calculated based on the obtained measured values ​​and the following formula.

[0330] (The content of a specific element in all solid components of the composition) = (The content of the specific element in the composition) × 100 / (The concentration of solid components in the composition [mass%])

[0331] Combustion and Absorption Conditions

[0332] System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation)

[0333] Electric furnace temperature: Inlet 900℃, Outlet 1000℃

[0334] Gases: Ar / O2 200 mL / min, O2 400 mL / min

[0335] Absorbent: H2O2 0.1% by mass

[0336] Absorption liquid volume: 5 mL

[0337] <Ion Chromatography and Anion Analysis Conditions>

[0338] System: ICS1600 (manufactured by Dionex)

[0339] Shift phase: 2.7 mmol / L Na₂CO₃, 0.3 mmol / L NaHCO₃

[0340] Flow rate: 1.50 mL / min

[0341] Detector: Conductivity detector

[0342] Injection volume: 100 μL.

[0343] (6) Production of raised patterns

[0344] Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron, Inc.), the photosensitive resin compositions obtained in the various examples and comparative examples were coated onto an 8-inch silicon wafer by spin coating, and heated at 100°C for 2 minutes to produce a photosensitive resin film with a thickness of 4.0 μm. Furthermore, the film thickness was measured using a Lambda Ace STM-602 optical interferometry film thickness measuring apparatus (manufactured by SCREEN Holdings, Inc.) at a refractive index of 1.629. Subsequently, using an i-ray stepper NSR-2005i9C exposure machine (manufactured by Nikon Corporation), a mask with a pattern of 10 μm contact holes was used at an exposure dose of 5 mJ / cm². 2 ~300 mJ / cm 2 Every 5 mJ / cm 2 Exposure is performed. After exposure, the mixture is heated at 170°C for 30 minutes. Using the developing apparatus of the ACT-8, 2.38% by mass of tetramethylammonium hydroxide (TMAH) (manufactured by Tama Chemical Industry Co., Ltd.) is used as the developing solution. After developing for 80 seconds, the mixture is rinsed with distilled water, spun dry, and heated at 310°C for 10 minutes to obtain a raised pattern.

[0345] (6-1) Calculation of the reduction in the amount of developing film

[0346] The reduction in film thickness is calculated by subtracting the film thickness after development from the film thickness before development in the unexposed area. The results are judged as follows, and those with a film reduction of less than 0.4 μm, from A+ to B, are considered acceptable.

[0347] A+: The reduction in membrane size is less than 0.15 μm.

[0348] A: The reduction in membrane size is greater than 0.15 μm and less than 0.2 μm.

[0349] B+: The reduction in membrane size is greater than 0.2 μm and less than 0.3 μm.

[0350] B: The reduction in membrane size is greater than 0.3 μm and less than 0.4 μm.

[0351] C: The reduction in the size of the developing film is greater than 0.4 μm.

[0352] (6-2) Sensitivity

[0353] Regarding sensitivity, the embossed pattern was observed at 20x magnification using an MX61 flat panel display (FPD) microscope (manufactured by Olympus Corporation), and the aperture diameter of the contact hole was measured. The minimum exposure required for the contact hole aperture diameter to reach 10 μm was determined and set as the sensitivity. The results were judged as follows, with a sensitivity of less than 200 mJ / cm². 2 A+ to B- are set as qualified.

[0354] A+: Sensitivity less than 85 mJ / cm 2

[0355] A: Sensitivity is 85 mJ / cm 2 Above and less than 100 mJ / cm 2

[0356] A-: Sensitivity is 100 mJ / cm 2 Above and less than 120 mJ / cm 2

[0357] B+: Sensitivity is 120 mJ / cm 2 Above and less than 140 mJ / cm 2

[0358] B: Sensitivity is 140 mJ / cm 2 Above and less than 170 mJ / cm 2

[0359] B-: Sensitivity is 170 mJ / cm 2 Above and less than 200 mJ / cm 2

[0360] C: Sensitivity is 200 mJ / cm 2 above.

[0361] (7) Glass transition temperature

[0362] Using a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments, Inc., with the nitrogen flow rate set to 40 mL / min and liquid nitrogen used for cooling, 5 mg of the hardened material recovered from the obtained embossed pattern was measured into an aluminum pan. Using an empty aluminum pan as a reference, the heat was measured according to the following sequence.

[0363] (3-1) After adjusting to 30℃, increase the temperature from 30℃ to 100℃ at a rate of 10℃ / minute.

[0364] (3-2) Keep at 100℃ for 5 minutes.

[0365] (3-3) Heat from 100℃ to 500℃ at a heating rate of 10℃ / min.

[0366] If baseline shift is confirmed in (3-3) above, the temperature at the intersection of the baseline on the low-temperature side and the tangent at the inflection point is set as the glass transition point. The results are judged as follows, and A+ to B with a glass transition temperature of 200°C or higher are deemed acceptable.

[0367] A+: Glass transition temperature above 350℃

[0368] A: Glass transition temperature is above 300℃ and below 350℃

[0369] B+: Glass transition temperature is above 250℃ and below 300℃

[0370] B: Glass transition temperature is above 200℃ and below 250℃

[0371] C: Glass transition temperature less than 200℃.

[0372] (8) The amount of (b) amine compounds remaining in the hardened film

[0373] Under the following apparatus structure and measurement conditions, the hardened material recovered from the obtained embossed pattern was subjected to gas chromatography to determine the fragment strength of the (b)amine compound. A calibration curve relating the amount of (b)amine compound added to the fragment strength was separately prepared to evaluate the residual amount of (b)amine compound in the hardened material.

[0374] [Device Structure]

[0375] Agilent-manufactured 6890 / 5973N

[0376] JHP-3S Curie-point pyrolyzer manufactured by Japan Analysis Industries Co., Ltd.

[0377] G / C column: HP-5ms 30 m nonpolar (capillary column with polydimethylsiloxane as the stationary layer) manufactured by Agilent.

[0378] [Measurement Conditions]

[0379] Carrier gas: He (80 MPa)

[0380] Thermal decomposition: The sample is heated to 400℃ (decomposition chamber temperature 280℃).

[0381] Tube column chamber: After holding at 40°C for 5 minutes, heat to 350°C at a rate of 10°C / min, and hold at 350°C for 20 minutes.

[0382] Quality analysis: Electron impact ionization (EI), ionization voltage 70 eV, ionization chamber temperature 200℃

[0383] Quad-pole mass selectable, quad-pole chamber temperature 150℃.

[0384] Synthesis Example 1: Synthesis of polyamide, i.e., polyimide precursor (PA-1)

[0385] 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-necked flask. 26.48 g (90 mmol) of BPDA (as an acid dianhydride) and 40 g of NMP were added together, and the mixture was stirred at 40°C for 1 hour. Then, 2.96 g (20 mmol) of phthalic anhydride and 40 g of NMP were added, 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 added to 2 L of pure water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and dried under vacuum at 40°C for 4 hours to obtain a polyamide, i.e., a polyimide precursor (PA-1), powder. The obtained resin had a Mw of 27,400 and an acid equivalent of 240 g / mol.

[0386] Synthesis Examples 2-3: Synthesis of polyamide, i.e., polyimide precursors (PA-2-PA-3)

[0387] Except for changing the amine derivative, carboxylic acid derivative, and capping agent from those in Synthesis Example 1 to the types and amounts listed in Table 1, the same method as in Synthesis Example 1 was used. The Mw and acid equivalent of the obtained resin are listed in Table 1.

[0388] Synthesis Example 4: Synthesis of polyamide, i.e., polyimide precursor (PA-4)

[0389] Under a dry nitrogen atmosphere, 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) and 50 g of NMP were added together, and the mixture was stirred at 40 °C for 2 hours. Then, 2.96 g (20 mmol) of phthalic anhydride and 50 g of NMP were added together, and the reaction was carried out at 50 °C for 2 hours. Subsequently, a solution prepared by diluting 23.8 g (200 mmol) of N,N-dimethylformamide dimethylacetal (DFA) with 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was added to 2 L of pure water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain polyamide, i.e., polyimide precursor (PA-4) powder. The obtained resin had a Mw of 27,000 and an acid equivalent of 440 g / mol.

[0390] Synthesis Examples 5-6: Synthesis of polyamide, i.e., polyimide precursors (PA-5-PA-6)

[0391] Except for changing the amine derivative, carboxylic acid derivative, capping agent, and esterifying agent to those listed in Table 1, the same method as in Synthesis Example 4 was used. The Mw and acid equivalent of the obtained resin are listed in Table 1.

[0392] Synthesis Example 7: Synthesis of Polyimide (PI-1)

[0393] 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-necked flask. 26.48 g (90 mmol) of BPDA (as an acid dianhydride) and 40 g of NMP were added together, and the mixture was stirred at 40 °C for 1 hour. Then, 2.96 g (20 mmol) of phthalic anhydride and 40 g of NMP were added, 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 added to 2 L of pure water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and dried in a vacuum dryer at 200 °C for 4 hours to obtain polyimide (PI-1) powder. The obtained resin had a Mw of 27,800 and an acid equivalent of 2,500 g / mol.

[0394] Synthesis Example 8: Synthesis of Polyimide (PI-2)

[0395] Except for changing the amine derivative, carboxylic acid derivative, and capping agent from those in Synthesis Example 7 to the types and amounts listed in Table 1, the same method was used as in Synthesis Example 7. The Mw and acid equivalent of the obtained resin are listed in Table 1.

[0396] Synthesis Example 9: Synthesis of polyamide, i.e., polybenzoxazole precursor (PA-7)

[0397] Under a dry nitrogen stream, 180 mmol of 4,4'-biphenyldicarboxylic acid and 360 mmol of a dicarboxylic acid derivative obtained by reacting it with 1-hydroxy-1,2,3-benzotriazole were reacted to obtain 180 mmol of a mixture of dicarboxylic acid derivatives. The resulting mixture (180 mmol), DABP (130 mmol), and DADHBP (70 mmol) were dissolved in 570 g of NMP, and the reaction was carried out at 75 °C for 12 h. Next, 40 mmol of phthalic anhydride dissolved in 70 g of NMP was added, and the mixture was stirred for another 12 h to terminate the reaction. After filtration, the reaction mixture was added to a solution of water / methanol = 3 / 1 (volume ratio), yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried under vacuum at 80 °C for 24 h to obtain an alkali-soluble resin (a-8) containing the target polybenzoxazole precursor. A polyamide, specifically a polybenzoxazole precursor (PA-7), was obtained as a powder. The resulting resin had a molecular weight (Mw) of 25,000 and an acid equivalent of 460 g / mol.

[0398] Synthesis Example 10: Synthesis of polyamide, i.e., polybenzoxazole precursor (PA-8)

[0399] Except for changing the amine derivative, carboxylic acid derivative, and capping agent from those in Synthesis Example 9 to the types and amounts listed in Table 1, the same method was used as in Synthesis Example 9. The Mw and acid equivalent of the obtained resin are listed in Table 1.

[0400] Synthesis Example 11: Synthesis of Polybenzoxazole (PBO-1)

[0401] 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 containing 34.89 g (125 mmol) of BPDCC dissolved in 30 g of NMP was added dropwise, ensuring the temperature of the reaction system did not exceed 0°C. After the addition was complete, the mixture was stirred at 20°C for 6 hours. After the reaction was complete, the solution was added to 3 L of pure water containing 10% methanol, causing a white precipitate to form. The precipitate was collected by filtration, washed three times with pure water, and then dried under vacuum at 200°C for 4 hours to obtain polybenzoxazole (PBO-1). The obtained resin had a Mw of 18,700 and an acid equivalent of 450 g / mol.

[0402] Synthesis Example 12: Synthesis of Polybenzoxazole (PBO-2)

[0403] Except for changing the amine derivative, carboxylic acid derivative, and capping agent from those in Synthesis Example 11 to the types and amounts listed in Table 1, the same method as in Synthesis Example 11 was used. The Mw and acid equivalent of the obtained resin are listed in Table 1.

[0404] Synthesis Example 13: Synthesis of Polyamide-Imine (PAI-1)

[0405] Regarding Synthesis Example 13, based on the method described in Synthesis Example 9 of International Publication No. 2018 / 159384, paragraph

[0160] , it is appropriate to change the monomeric compound or copolymerization ratio as a monomer, and synthesize it by a known method. The amine derivative, carboxylic acid derivative, and capping agent are used as described in Table 1, and the Mw and acid equivalent of the obtained resin are listed in Table 1.

[0406] [Table 1]

[0407]

[0408] Example 1

[0409] Under a yellow light, 2.50 g of PA-1 as (a) resin, 2.50 g of HA as (b) amine compound, 0.20 g of PAG-103 as (c) photoacid generator, and 30 g of CP as solvent were added and stirred to prepare a photosensitive resin composition.

[0410] The preparation of the photosensitive resin composition was carried out to create (2) a raised pattern, and to evaluate (2-1) the reduction in developing film, (2-2) the sensitivity, (3) the glass transition temperature, and (4) the residual amount of (b) amine compounds in the hardened film. The evaluation results are shown in Tables 2 to 3.

[0411] Examples 2-36, Comparative Examples 1-4

[0412] Except for changing (a) the resin, (b) the amine compound, (c) the photoacid generator, and CP in the photosensitive resin composition to the types and amounts described in Tables 2 and 3, the evaluation was conducted in the same manner as in Example 1. The evaluation results are shown in Tables 2 and 3. Furthermore, in Examples 33 to 36, the fluorine-containing compounds, namely Fc-1 and FI-1, were added in such a manner that the content of fluorine in all solid components of the photosensitive resin composition was as shown in Table 3. In addition, in Examples 1 to 32 and Comparative Examples 1 to 4, the content of fluorine in all solid components of the photosensitive resin composition was 0 ppm by mass.

[0413] Furthermore, in Comparative Example 1, the content of (b) amine compound did not meet the specific inventive claims of this invention. In Comparative Example 2, (b) amine compound did not contain either a primary or secondary amine. Therefore, it was found that the various properties of Comparative Examples 1 and 2 were poor. In addition, in Comparative Examples 3 and 4, the photosensitive resin composition did not contain (b) amine compound or (c) photoacid generator. Therefore, it was found that Comparative Examples 3 and 4 could not form patterns and did not achieve the effects of this invention.

[0414] [Table 2]

[0415]

[0416] [Table 3]

[0417]

[0418] Industrial availability

[0419] This invention is suitable for use in photosensitive resin compositions that exhibit excellent heat resistance, minimal film reduction during development, and high sensitivity.

Claims

1. A photosensitive resin composition comprising: (a) A resin selected from the group consisting of polyimide, polyamide-imide, polybenzoxazole, and precursors thereof (hereinafter referred to as "(a) resin") (b) amine compounds, and (c) Photoacid generator, The amine compound in (b) is a primary or secondary amine. The photosensitive resin composition contains at least 35 parts by mass of the amine compound (b) relative to 100 parts by mass of the resin (a).

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 resin in (a) has a carboxylic acid equivalent of 500 g / mol or more, or the resin in (a) does not have a carboxyl group.

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

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

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

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

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

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

9. The photosensitive resin composition according to any one of claims 1 to 5, wherein the boiling point of the (b) amine compound at 1 atmosphere is above 100°C and below 300°C.

10. The photosensitive resin composition according to claim 1, wherein the resin (a) has electron-withdrawing groups, The resin (a) comprises selected from (a1) includes the polyimide or polyamide-imide (hereinafter referred to as "(a1) resin") that is a constituent unit represented by formula (1). (a2) includes the polyimide precursor or polyamide-imide precursor of the constituent unit represented by formula (2) (hereinafter referred to as "(a2) resin"). (a3) includes the polyamide-imide (hereinafter referred to as "(a3) resin") that is the constituent unit represented by formula (3). (a4) includes the polybenzoxazole (hereinafter referred to as "(a4) resin"), which is a constituent unit represented by formula (4), and (a5) includes the polybenzoxazole precursor of the constituent unit represented by formula (5) (hereinafter referred to as "(a5) resin") One or more resins in the group. [Chemistry 1] (In formula (1), L) 1 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 1 In X 1 ~X 4 Any position in, and X 5 ~X 8 Connect at any point in X. n (n=1~8) are CR n (n=1~8). R n (n=1~8) are groups of groups independently selected from hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, In L 1 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=2~3, 6~7) have electron-withdrawing groups. (Indicates the bonding location.) [Chemistry 2] (In formula (2), L) 2 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 2 In X 11 ~X 14 Any position in, and X 15 ~X 18 Connect at any point in X. n (n=11~18) are CR n (n=11~18). R n (n=9~18) are groups independently selected from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 2 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=12~13, 16~17) have electron-withdrawing groups. (Indicates the bonding location.) [Chemistry 3] (In formula (3), L) 3 It is an amide bond. L 3 With X 19 ~X 22 Link to any position in X. n (n=19~22) are CR n (n=19~22). R n (n=19~22) are groups selected independently from the group consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. R n One or more of the ones in (n=20~21) have electron-withdrawing groups. (Indicates the bonding location.) [Chemistry 4] (In equation (4), L) 4 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 4 In X 31 ~X 35 Any position in, and X 36 ~X 40 Connect at any point in X. n (n=23~40) are CR n (n=23~40). R n (n=23~40) are groups independently selected from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 4 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of (n=33, 38) have electron-withdrawing groups. 1 With X 23 ~X 26 Link any position in the string. 2 With X 27 ~X 30 Link any position in the string. 1 and 2 (Indicates the bonding location.) [Chemistry 5] (In equation (5), L) 5 It is a single bond, sulfonyl group, >C(CF3)2, oxygen atom, or a divalent organic group with 1 to 20 carbon atoms. L 5 In X 49 ~X 53 Any position in, and X 54 ~X 58 Connect at any point in X. n (n=41~58) are CR n (n=41~58). R n (n=41~58) are groups selected independently from those consisting of hydrogen atoms, electron-withdrawing groups, and monovalent organic groups with 1 to 20 carbon atoms. Among them, in L... 5 In the case that it is neither sulfonyl nor >C(CF3)2, R n One or more of the following (n=51, 58) have electron-withdrawing groups. 3 With X 41 ~X 44 Link any position in the string. 4 With X 45 ~X 48 Link any position in the string. 3 and 4 (Indicates the bonding location).

11. The photosensitive resin composition according to claim 10, wherein when the (a) resin has the (a1) resin, R n Any one or more of the groups (n=1~8) have electron-withdrawing groups. In the case where resin (a) has resin (a2), R n Any one or more of the groups (n=11~18) have electron-withdrawing groups. In the case where resin (a) has resin (a3), R n Any one or more of the groups (n=19~22) have electron-withdrawing groups. In the case where resin (a) has resin (a4), R n Any one or more of the groups (n=23~40) have electron-withdrawing groups. In the case where resin (a) has resin (a5), R n One or more of the ones in (n=41~58) have electron-withdrawing groups.

12. The photosensitive resin composition according to any one of claims 1 to 5, 10 and 11, wherein at least one of the following conditions (P1α) and the following condition (1α) is satisfied. (P1α) The content of fluorine in the structure of (a) resin is less than 10,000 ppm by mass; (1α) The content of fluorine in all solid components of the photosensitive resin composition is less than 1,000 ppm by mass.

13. The photosensitive resin composition according to any one of claims 1 to 5, 10 and 11, wherein the amine compound (b) is an amine salt. The amine salt is a compound containing a cationic species having a primary amine structure or a secondary amine structure, as well as an anionic species.

14. A method for manufacturing a pattern, comprising: The process of coating a substrate with the photosensitive resin composition as described in any one of claims 1 to 5, 10 and 11; The process of exposing the coated material to a light-blocking mask; The process of heating the coated material during or after exposure of the photomask; The process of developing the heated coating; and The process of heating the developed coating.

15. A cured material, formed by curing the photosensitive resin composition as described in any one of claims 1 to 5, 10 and 11.

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

17. An electronic component having the hardened material as described in claim 15.

18. A display device having the hardened material as described in claim 15.

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