Photosensitive resin compositions, photosensitive sheets, cured films, methods for manufacturing cured films, electronic components, antenna elements, semiconductor packaging, and display devices.

Abstract

The object of the present invention is to provide a photosensitive resin composition with excellent residual film rate after development, which can be cured by heat treatment at low temperature, and can obtain a cured film with excellent heat resistance, elongation, chemical resistance, dielectric constant, and dielectric loss tangent. In order to solve the above-mentioned problems, the photosensitive resin composition of the present invention has the following structure. That is, the photosensitive resin composition contains a resin (A) and a photopolymerization initiator (B), wherein the resin (A) comprises one or more structural units selected from the group consisting of structural units represented by specific formulas (1), (3), and (5), and further comprises one or more structural units selected from the group consisting of structural units represented by formulas (2), (4), and (6).

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, photosensitive sheets, cured films, methods for manufacturing cured films, antenna elements, semiconductor packages, electronic components, and display devices. More specifically, it relates to photosensitive resin compositions suitable for use as surface protective films, interlayer insulating films, insulating layers for organic EL elements, and the like in electronic components such as semiconductor elements. Background Technology

[0002] Polyimide resins, which possess excellent heat resistance and electrical insulation properties, are representative materials used in surface protective films for semiconductor devices, interlayer insulating films, insulating layers for organic electric field devices, and planarization films for TFT substrates. Furthermore, to improve productivity, research has also been conducted on photosensitive polyimides and their precursors that impart negative photosensitivity.

[0003] In recent years, with the expansion of semiconductor applications and the improvement of performance, efforts have been made to reduce costs and increase integration through the efficiency of manufacturing processes. Therefore, semiconductor devices with multilayer metal rewiring have attracted attention. For such multilayer metal rewiring insulating films, a low dielectric constant is required to accompany high integration. Furthermore, in high-frequency communication devices used for high-speed wireless communication, a low dielectric loss tangent is required for the insulating film to reduce transmission loss. In addition, considering that memory devices used in recent years and molding resins used in semiconductor packaging are not resistant to high-temperature processes, surface protective films and interlayer insulating films require polyimide resins and polybenzoxazole resins that can be cured by firing at low temperatures below 250°C (more preferably below 220°C) and have high mechanical properties, thermal properties, and chemical resistance.

[0004] Examples of methods for reducing dielectric constant and dielectric loss tangent include photosensitive resin compositions formed by introducing specific chemical structures into a portion of the side chains of a polyimide precursor (Patent Document 1) and soluble polyimides using dimeric diamines (Patent Document 2). Examples of resin compositions capable of low-temperature curing include resin compositions comprising resins such as polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole, and a thermal crosslinking agent (Patent Document 3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2019 / 044874

[0008] Patent Document 2: Japanese Patent Application Publication No. 2018-203959

[0009] Patent document 3: Japanese Patent Application Publication No. 2007-16214. Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] When using existing technology as a multilayer wiring insulating film for high-frequency communication devices used in high-speed wireless communication, the following problems exist: For example, in Patent Document 1, the chemical resistance and mechanical properties are insufficient due to insufficient imide ring closure during low-temperature curing; in Patent Document 2, the heat resistance and sufficient residual film rate after development cannot be obtained due to the soft skeleton derived from dimeric diamine; and in Patent Document 3, the dielectric loss tangent is high.

[0012] Methods for solving problems

[0013] To address the aforementioned issues, the present invention is as follows.

[0014] (1) A photosensitive resin composition comprising a resin (A1) and a photopolymerization initiator (B), wherein the resin (A1) is a resin having a structural unit represented by general formula (17) and having an olefinic unsaturated bond, comprising at least one selected from polyimide, polybenzoxazole, their precursors and copolymers thereof, wherein the precursor also has bonds derived from olefinic unsaturated bonds after imidization or oxazoleization.

[0015] [Chemical Formula 1]

[0016]

[0017] In equation (17), c, d, e and f are integers above 1 that satisfy c+d = 6 to 17 and e+f = 8 to 19. The dashed part refers to carbon-carbon single bonds or carbon-carbon double bonds.

[0018] (2) A photosensitive resin composition comprising a resin (A2) and a photopolymerization initiator (B), wherein the resin (A2) has at least one of the structural units represented by formulas (18), (19), and (20) and has a structural unit represented by formula (17).

[0019] [Chemical Formula 2]

[0020]

[0021] In equation (17), c, d, e and f are integers above 1 that satisfy c+d = 6 to 17 and e+f = 8 to 19. The dashed part refers to carbon-carbon single bonds or carbon-carbon double bonds.

[0022] [Chemical Formula 3]

[0023]

[0024] In equation (18), X8 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 8 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 19 and R 20 Each of the following groups independently represents a carboxyl group, a hydroxyl group, or an organic group with 3 to 30 monovalent carbon atoms having an alkene-type unsaturated bond; R 19 and R 20 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, g represents an integer from 0 to 2, h represents an integer from 0 to 4, 1≤g+h≤6, and * represents a bonding point.

[0025] [Chemical Formula 4]

[0026]

[0027] In equation (19), X 9 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 9 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 21 and R 22 They can be the same or different, representing a carboxyl group, hydroxyl group, or an organic group with 3 to 30 carbon atoms in a monovalent state and an alkene-type unsaturated bond, R. 21 and R 22 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, i represents an integer from 0 to 2, j represents an integer from 0 to 4, 1≤i+j≤6, and * represents a bonding point.

[0028] [Chemical Formula 5]

[0029]

[0030] In equation (20), X 10 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 10 Organic groups representing 2-70 carbon atoms with 2-6 valences (COOR) 23 ) is located at the same level as X 10 The position of the bonded amide group forming the imide ring is determined by the substituent, R. 23 R represents an organic group having 1 to 5 hydrogen or carbon atoms. 24 R represents a hydroxyl group or a monovalent organic group with an alkene-type unsaturated bond having 3 to 30 carbon atoms. 25 R represents a monovalent organic group consisting of a carboxyl group, a hydroxyl group, or an alkene-type unsaturated bond with 3 to 30 carbon atoms. 24 and R 25At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, k represents an integer from 0 to 2, x represents an integer from 0 to 2, y represents an integer from 0 to 4, 1≤x+y≤6, and * represents a bonding point.

[0031] (3) A photosensitive resin composition comprising a resin (A3) and a photopolymerization initiator (B), wherein the resin (A3) comprises one or more structural units selected from the group consisting of structural units represented by formula (1), formula (3) and formula (5), and further comprises one or more structural units selected from the group consisting of structural units represented by formula (2), formula (4) and formula (6).

[0032] [Chemical Formula 6]

[0033]

[0034] In equation (1), X 1 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 1 X represents a divalent organic group with 2 to 70 carbon atoms. 1 and Y 1 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are replaced by hydrocarbon groups having 4 to 12 carbon atoms that may have unsaturated bonds, and * indicates a bonding site.

[0035] [Chemical Formula 7]

[0036]

[0037] In equation (2), X 2 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 2 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 1 and R 2 Each of the following groups independently represents a carboxyl group, a hydroxyl group, or an organic group with 3 to 30 monovalent carbon atoms having an alkene-type unsaturated bond; R 1 and R 2 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, p represents an integer from 0 to 2, q represents an integer from 0 to 4, 1≤p+q≤6, and * represents a bonding point.

[0038] [Chemical Formula 8]

[0039]

[0040] In equation (3), X 3Y represents a tetravalent organic group with 2 to 60 carbon atoms. 3 X represents a divalent organic group with 2 to 70 carbon atoms. 3 and Y 3 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are replaced by hydrocarbon groups having 4 to 12 carbon atoms that may have unsaturated bonds, and * indicates a bonding site.

[0041] [Chemical Formula 9]

[0042]

[0043] In equation (4), X 4 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 4 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 3 and R 4 They can be the same or different, representing a carboxyl group, hydroxyl group, or an organic group with 3 to 30 carbon atoms in a monovalent state and an alkene-type unsaturated bond, R. 3 and R 4 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, r represents an integer from 0 to 2, s represents an integer from 0 to 4, 1≤r+s≤6, and * represents a bonding point.

[0044] [Chemical Formula 10]

[0045]

[0046] In equation (5), X 5 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 5 X represents a divalent organic group with 2 to 70 carbon atoms. 5 and Y 5 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are substituted by hydrocarbon groups having 4 to 12 carbon atoms that may have unsaturated bonds. (COOR) 5 ) is located at the same level as X 5 The position of the bonded amide group forming the imide ring is determined by the substituent, R. 5 This indicates an organic group with 1 to 5 hydrogen or carbon atoms, and * indicates a bonding point.

[0047] [Chemical Formula 11]

[0048]

[0049] In equation (6), X 6 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 6 Organic groups representing 2-70 carbon atoms with 2-6 valences (COOR) 6 ) is located at the same level as X 6 The position of the bonded amide group forming the imide ring is determined by the substituent, R. 6 R represents an organic group having 1 to 5 hydrogen or carbon atoms. 7 R represents a hydroxyl group or a monovalent organic group with an alkene-type unsaturated bond having 3 to 30 carbon atoms. 8 R represents a monovalent organic group consisting of a carboxyl group, a hydroxyl group, or an alkene-type unsaturated bond with 3 to 30 carbon atoms. 7 and R 8 At least one of them has an alkene-type unsaturated bond with 3 to 30 carbon atoms, t represents an integer from 0 to 2, u represents an integer from 0 to 4, 1≤t+u≤6, and * represents a bonding point.

[0050] The effects of the invention

[0051] The photosensitive resin composition of the present invention exhibits a high residual film yield after development. Furthermore, its cured film demonstrates excellent heat resistance, chemical resistance, dielectric constant, and dielectric loss tangent. Attached Figure Description

[0052] [ Figure 1 ] Figure 1 This is a diagram showing an enlarged cross-section of the pad portion of a semiconductor device with bumps.

[0053] [ Figure 2 ] Figure 2 A diagram illustrating a detailed fabrication process for a semiconductor device with bumps.

[0054] [ Figure 3 ] Figure 3 This is a schematic diagram of a coplanar powered microstrip antenna, which is one type of planar antenna.

[0055] [ Figure 4 ] Figure 4 This is a schematic diagram relating to a cross-section of a semiconductor package containing an IC chip (semiconductor element), redistribution, sealing resin, and antenna elements. Detailed Implementation

[0056] The photosensitive resin composition of the present invention contains a resin (A1) (hereinafter, sometimes simply referred to as "(A1) component") and a photopolymerization initiator (B) (hereinafter, sometimes simply referred to as "(B) component"). The resin (A1) is a resin having a structural unit represented by general formula (17) and having olefinic unsaturated bonds, comprising at least one selected from polyimide, polybenzoxazole, their precursors and copolymers thereof. The precursors also have bonds derived from olefinic unsaturated bonds after imidization or oxazoleization.

[0057] [Chemical Formula 12]

[0058]

[0059] In equation (17), c, d, e and f are integers above 1 that satisfy c+d = 6 to 17 and e+f = 8 to 19. The dashed part refers to carbon-carbon single bonds or carbon-carbon double bonds.

[0060] Here, when expressed as “~” in this specification, unless otherwise specified, it refers to a number that includes its upper and lower limits.

[0061] Resins with cyclic structures consisting of an imide ring or an oxazole ring in the main chain, such as polyimide and polybenzoxazole. Furthermore, the polyimide precursor and polybenzoxazole precursor, which are their precursors, are resins that form imide rings and benzoxazole rings respectively through dehydration and ring closure.

[0062] Polyimides can be obtained by reacting tetracarboxylic acids, tetracarboxylic dianhydrides, tetracarboxylic acid diesters, etc., with diamines, diisocyanate compounds, trimethylsilyldiamine, etc., and thus possessing tetracarboxylic acid residues and diamine residues. For example, polyamic acid, obtained by reacting tetracarboxylic dianhydrides with diamines and serving as a polyimide precursor, can be dehydrated and ring-closed by heat treatment to obtain polyimides. During this heat treatment, a solvent that azeotropically reacts with water, such as m-xylene, can also be added. Alternatively, a ring-closing catalyst, such as a carboxylic anhydride, dicyclohexylcarbodiimide, or a base, can be added, and dehydration and ring closure can be achieved through chemithermal treatment. Furthermore, a weakly acidic carboxylic acid compound can be added, and dehydration and ring closure can be achieved through heat treatment at a low temperature below 100°C.

[0063] Alternatively, copolymers can also be produced by adjusting the reaction time during the above-mentioned dehydration and ring-closing process and by continuing to polymerize polyamic acid after polymerizing polyimide.

[0064] Known materials can be used as tetracarboxylic dianhydrides. Examples include butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, dicyclohexanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxophthalic anhydride, p-phenylenebis(triphenylene oxide), ethylene glycol dihydrotriphenylene oxide, and 4,4'-(hexafluoroisopropylene)phthalic anhydride. These compounds can be used alone or in combination of two or more.

[0065] Known materials can be used as diamines. Examples include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, o-triazine, 4,4”-diaminoterphenyl, 1,5-diaminonaphthalene, 2,5-diaminopyridine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis(p-aminophenoxy)biphenyl, 2,2-bis[4-(p-aminophenoxy)phenyl]propane, and hexahydro-4,7-methanol-4,7-bridged methyleneindimethylenediamine. These compounds can be used alone or in combination of two or more.

[0066] Polybenzoxazole can be obtained by reacting diaminophenol compounds with dicarboxylic acids, dicarboxyl chlorides, or reactive dicarboxylic acid esters, and contains both dicarboxylic acid and diaminophenol residues. For example, polyhydroxyamide, obtained by reacting diaminophenol compounds with dicarboxylic acids and serving as a precursor of polybenzoxazole, can be dehydrated and ring-closed by heat treatment to obtain polybenzoxazole. Alternatively, dehydration and ring-closure can be achieved through chemical treatment by adding phosphoric anhydride, alkali, or carbodiimide compounds.

[0067] Alternatively, copolymers can also be produced by adjusting the reaction time during the above-mentioned dehydration and ring-closing process and by continuing to polymerize polyhydroxyamides after polymerizing polybenzoxazole.

[0068] Known materials can be used as dicarboxylic acids. Examples include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, pyromellitic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. These compounds can be used alone or in combination of two or more.

[0069] Known materials can be used as diaminophenol compounds. Examples include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc., but are not limited to these. These compounds can be used alone or in combination of two or more.

[0070] Alternatively, copolymers containing two or more of the following can be prepared by combining tetracarboxylic dianhydride, dicarboxylic acid, and diamine: polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

[0071] The aforementioned precursors also possess olefinic unsaturated bonds after imidization or oxazoleization. By possessing olefinic unsaturated bonds after imidization or oxazoleization, improved heat resistance due to crosslinking of the resins can be imparted during curing.

[0072] As a method for introducing olefinic unsaturated bonds into a resin, known methods include: reacting hydroxyl and / or carboxyl groups in the resin with a compound having olefinic unsaturated double bond groups; polymerizing a monomer having olefinic unsaturated bonds to obtain a resin; and so on. From a reactivity point of view, electrophilic compounds having olefinic unsaturated double bond groups are preferred as compounds having olefinic unsaturated double bond groups.

[0073] Examples of electrophilic compounds include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thionone compounds, acetate compounds, carboxyl chlorides, carboxylic anhydrides, carboxylic acid reactive ester compounds, carboxylic acid compounds, haloalkyl compounds, azidoalkyl compounds, trifluoromethanesulfonate alkyl compounds, methanesulfonate alkyl compounds, toluenesulfonate alkyl compounds, or cyanide alkyl compounds. From the viewpoint of reactivity and the usability of the compound, isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds, or carboxylic anhydrides are preferred, and isocyanate compounds, epoxy compounds, and carboxylic anhydrides are more preferred.

[0074] To prevent cross-linking of the olefinic unsaturated bond sites during the reaction, a small amount of polymerization inhibitor may be used. Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, tert-butylcatechol, and bis-tert-butylhydroxytoluene. The amount of polymerization inhibitor added is preferably 0.1 mol% to 5 mol% of phenolic hydroxyl groups relative to the olefinic unsaturated bond of the alcohol.

[0075] Formula (17) is a structure with a dimer framework (i.e., dimers of unsaturated fatty acids such as linoleic acid and oleic acid). From the viewpoint of the reliability of the obtained cured film, a structure without double bonds is preferred.

[0076] For specific examples of diamines having the structure represented by formula (17), commercially available diamines include “Versamine 551” and “Versamine 552” manufactured by BASF Corporation, and “Priamine 1073”, “Priamine 1074” and “Priamine 1075” manufactured by Claude Japan Corporation. Here, “Versamine 551” and “Priamine 1074” are diamine compounds that include the compound represented by formula (10), and “Versamine 552”, “Priamine 1073” and “Priamine 1075” are diamine compounds that include the compound represented by formula (9).

[0077] [Chemical Formula 13]

[0078]

[0079] [Chemical Formula 14]

[0080]

[0081] Alternatively, a mixture of melamine and dimericane can be used. Commercially available products containing melamine and dimericane include "Priamine (registered trademark) 1071" manufactured by Claude Japan Co., Ltd.

[0082] For specific examples of polycarboxylic acids having the structure represented by formula (17), examples include “Pripol (registered trademark)” 1009, “Pripol (registered trademark)” 1006, “Pripol (registered trademark)” 1010, “Pripol (registered trademark)” 1013, “Pripol (registered trademark)” 1025, “Pripol (registered trademark)” 1017, “Pripol (registered trademark)” 1040, and “Pripol (registered trademark)” 1004, etc., manufactured by Claude Japan Co., Ltd.

[0083] As derivatives of polycarboxylic acids having the structure represented by formula (17), examples of the above-mentioned diamines and reactants of trimellitic anhydride acyl chlorides can be cited. More specifically, it is shown in formula (11).

[0084] [Chemical Formula 15]

[0085]

[0086] In equation (11), i', j', k', and l' are natural numbers, i'+j' = 6 to 17, and k'+l' = 8 to 19. The dashed part refers to carbon-carbon single bonds or carbon-carbon double bonds.

[0087] In resin (A1), the content of the structural unit represented by formula (17) is preferably 1 mol% or more and 30 mol% or less, more preferably 1 mol% or more and 15 mol% or less. A content of 1 mol% or more reduces the relative permittivity and dielectric loss tangent. Furthermore, a content of 30 mol% or less improves heat resistance.

[0088] The photosensitive resin composition of the present invention contains a resin (A2) (hereinafter sometimes simply referred to as "(A2) component") and a photopolymerization initiator (B), wherein the resin (A2) has any one of the structural units represented by formula (18), (19), and (20) and has a structural unit represented by formula (17).

[0089] [Chemical Formula 16]

[0090]

[0091] In equation (18), X 8 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 8 Organic groups with 2 to 70 carbon atoms and 2 to 6 valences, containing multiple R groups. 19 and R 20 Each of the following groups independently represents a carboxyl group, a hydroxyl group, or an organic group with 3 to 30 monovalent carbon atoms having an alkene-type unsaturated bond; R 19 and R 20 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, g represents an integer from 0 to 2, h represents an integer from 0 to 4, 1≤g+h≤6, and * represents a bonding point.

[0092] [Chemical Formula 17]

[0093]

[0094] In equation (19), X 9 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 9Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 21 and R 22 They can be the same or different, representing a carboxyl group, hydroxyl group, or an organic group with 3 to 30 carbon atoms in a monovalent state and an alkene-type unsaturated bond, R. 21 and R 22 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, i represents an integer from 0 to 2, j represents an integer from 0 to 4, 1≤i+j≤6, and * represents a bonding point.

[0095] [Chemical Formula 18]

[0096]

[0097] In equation (20), X 10 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 10 Organic groups representing 2-70 carbon atoms with 2-6 valences (COOR) 23 ) is located at the same level as X 10 The position of the bonded amide group forming the imide ring is determined by the substituent, R. 23 R represents an organic group having 1 to 5 hydrogen or carbon atoms. 24 R represents a hydroxyl group or a monovalent organic group with an alkene-type unsaturated bond having 3 to 30 carbon atoms. 25 R represents a monovalent organic group consisting of a carboxyl group, a hydroxyl group, or an alkene-type unsaturated bond with 3 to 30 carbon atoms. 24 and R 25 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, k represents an integer from 0 to 2, x represents an integer from 0 to 2, y represents an integer from 0 to 4, 1≤x+y≤6, and * represents a bonding point.

[0098] An organic group is a group that contains at least a carbon atom, and may further contain oxygen, hydrogen, fluorine, and other atoms as needed. Furthermore, an organic group with an X valence is a group whose chemical structure is formed by the organic compound becoming an X-valence group; it refers to an atomic group formed by removing X hydrogen atoms from an organic compound.

[0099] With respect to the photosensitive resin composition of the present invention, by including component (A2), the cured film of the present invention formed by curing the photosensitive resin composition of the present invention becomes a film with low dielectric constant and low dielectric loss tangent.

[0100] In equations (18), (19), and (20), X 8 X 9 and X 10This refers to a tetravalent organic group with 2 to 60 carbon atoms, and a residue representing an acid component. Examples of acid components include tetracarboxylic acids, tetracarboxylic dianhydrides, and tetracarboxylic acid diesters and dichlorides.

[0101] Y 8 Y 9 and Y 10 It represents a divalent organic group with 2 to 70 carbon atoms, and represents an amine residue.

[0102] In resin (A2), the content of the structural unit represented by formula (17) is preferably 1 mol% or more and 30 mol% or less, more preferably 1 mol% or more and 15 mol% or less. A content of 1 mol% or more reduces the relative permittivity and dielectric loss tangent. Furthermore, a content of 30 mol% or less improves heat resistance.

[0103] By using R in the above equation (18) 19 and R 20 R of equation (19) 21 and R 22 R of equation (20) 24 and R 25 The presence of olefinic unsaturated bonds at any of the positions can impart an increase in heat resistance during curing due to the cross-linking of the resins.

[0104] As a method for introducing olefinic unsaturated bonds into a resin, known methods include: reacting hydroxyl and / or carboxyl groups in the resin with a compound having olefinic unsaturated double bond groups; polymerizing a resin using a monomer having olefinic unsaturated bonds; etc. From a reactivity point of view, electrophilic compounds having olefinic unsaturated double bond groups are preferred as compounds having olefinic unsaturated double bond groups.

[0105] Examples of electrophilic compounds include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thionone compounds, acetate compounds, carboxyl chlorides, carboxylic anhydrides, carboxylic acid reactive ester compounds, carboxylic acid compounds, haloalkyl compounds, azidoalkyl compounds, trifluoromethanesulfonate alkyl compounds, methanesulfonate alkyl compounds, toluenesulfonate alkyl compounds, or cyanide alkyl compounds. From the viewpoint of reactivity and the usability of the compound, isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds, or carboxylic anhydrides are preferred, and isocyanate compounds, epoxy compounds, and carboxylic anhydrides are more preferred.

[0106] To prevent cross-linking of the olefinic unsaturated bond sites during the reaction, a small amount of polymerization inhibitor may be used. Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, tert-butylcatechol, and bis-tert-butylhydroxytoluene. The amount of polymerization inhibitor added is preferably 0.1 mol% to 5 mol% of phenolic hydroxyl groups relative to the olefinic unsaturated bond of the alcohol.

[0107] The photosensitive resin composition of the present invention contains a resin (A3) (hereinafter sometimes simply referred to as "(A3) component") and a photopolymerization initiator (B). The resin (A3) contains one or more structural units selected from the group consisting of structural units represented by formula (1), formula (3) and formula (5), and also contains one or more structural units selected from the group consisting of structural units represented by formula (2), formula (4) and formula (6).

[0108] [Chemical Formula 19]

[0109]

[0110] In equation (1), X 1 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 1 X represents a divalent organic group with 2 to 70 carbon atoms. 1 and Y 1 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are replaced by hydrocarbon groups having 4 to 12 carbon atoms that may have unsaturated bonds, and * indicates a bonding site.

[0111] [Chemical Formula 20]

[0112]

[0113] In equation (2), X 2 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 2 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 1 and R 2 Each of the following groups independently represents a carboxyl group, a hydroxyl group, or an organic group with 3 to 30 monovalent carbon atoms having an alkene-type unsaturated bond; R 1 and R 2 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, p represents an integer from 0 to 2, q represents an integer from 0 to 4, 1≤p+q≤6, and * represents a bonding point.

[0114] [Chemical Formula 21]

[0115]

[0116] In equation (3), X 3 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 3 X represents a divalent organic group with 2 to 70 carbon atoms. 3 and Y 3 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are replaced by hydrocarbon groups having 4 to 12 carbon atoms that may have unsaturated bonds, and * indicates a bonding site.

[0117] [Chemical Formula 22]

[0118]

[0119] In equation (4), X 4 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 4 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 3 and R 4 They can be the same or different, representing a carboxyl group, hydroxyl group, or an organic group with 3 to 30 carbon atoms in a monovalent state and an alkene-type unsaturated bond, R. 3 and R 4 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, r represents an integer from 0 to 2, s represents an integer from 0 to 4, 1≤r+s≤6, and * represents a bonding point.

[0120] By having olefinic unsaturated bonds, it is possible to improve the residual film rate after development and to impart improved heat resistance during curing due to the cross-linking of the resins.

[0121] [Chemical Formula 23]

[0122]

[0123] In equation (5), X 5 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 5 X represents a divalent organic group with 2 to 70 carbon atoms. 5 and Y 5 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are substituted by hydrocarbon groups having 4 to 12 carbon atoms that may have unsaturated bonds. (COOR) 5 ) is located at the same level as X 5The position of the bonded amide group forming the imide ring is determined by the substituent, R. 5 This indicates an organic group with 1 to 5 hydrogen or carbon atoms, and * indicates a bonding point.

[0124] [Chemical Formula 24]

[0125]

[0126] In equation (6), X 6 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 6 Organic groups representing 2-70 carbon atoms with 2-6 valences (COOR) 6 ) is located at the same level as X 6 The position of the bonded amide group forming the imide ring is determined by the substituent, R. 6 R represents an organic group having 1 to 5 hydrogen or carbon atoms. 7 R represents a hydroxyl group or a monovalent organic group with an alkene-type unsaturated bond having 3 to 30 carbon atoms. 8 R represents a monovalent organic group consisting of a carboxyl group, a hydroxyl group, or an alkene-type unsaturated bond with 3 to 30 carbon atoms. 7 and R 8 At least one of them has an alkene-type unsaturated bond with 3 to 30 carbon atoms, t represents an integer from 0 to 2, u represents an integer from 0 to 4, 1≤t+u≤6, and * represents a bonding point.

[0127] With respect to the photosensitive resin composition of the present invention, by including component (A3), the cured film of the present invention formed by curing the photosensitive resin composition of the present invention becomes a film with low dielectric constant and low dielectric loss tangent.

[0128] In equations (1), (3), and (5), X 1 X 3 and X 5 This refers to a tetravalent organic group with 2 to 60 carbon atoms, and a residue representing an acid component. Examples of acid components include tetracarboxylic acids, tetracarboxylic dianhydrides, or tetracarboxylic acid diesters and dichlorides.

[0129] Y 1 Y 3 and Y 5 It represents a divalent organic group with 2 to 70 carbon atoms, and represents an amine residue.

[0130] X 1 and Y 1At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds (hereinafter sometimes simply referred to as "structure (a)"), wherein at least 4 or more hydrogen atoms in the alicyclic hydrocarbon structure are replaced by hydrocarbon groups with 4 to 12 carbon atoms that may have unsaturated bonds.

[0131] X 3 and Y 3 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds (hereinafter sometimes simply referred to as "structure (a)"), wherein at least 4 or more hydrogen atoms in the alicyclic hydrocarbon structure are replaced by hydrocarbon groups with 4 to 12 carbon atoms that may have unsaturated bonds.

[0132] X 5 and Y 5 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds (hereinafter sometimes simply referred to as "structure (a)"), wherein at least 4 or more hydrogen atoms in the alicyclic hydrocarbon structure are replaced by hydrocarbon groups with 4 to 12 carbon atoms that may have unsaturated bonds.

[0133] The cured film formed by curing the resin composition containing the above structure has high elongation, low dielectric constant, and low dielectric loss tangent.

[0134] Examples of structures (a) include cyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, and cyclooctenyl. Among these, cyclohexyl, cyclohexenyl, cycloheptyl, and cycloheptenyl are preferred from the viewpoint of thermal stability.

[0135] Examples of hydrocarbon groups that can have 4 to 12 carbon atoms with unsaturated bonds include n-butyl, isobutyl, tert-butyl, 1-butenyl, 2-butenyl, n-pentyl, isopentyl, 1-pentenyl, 2-pentenyl, n-hexyl, isohexyl, 1-hexenyl, 2-hexenyl, n-heptyl, isoheptyl, 1-heptenyl, 2-heptenyl, n-octyl, isooctyl, 1-octenyl, 2-octenyl, nonyl, 1-nonenyl, decyl, 1-decenyl, undecyl, 1-undecenyl, dodecyl, and 1-dodecenyl.

[0136] Examples of carboxylic acid compounds that become polycarboxylic acid residues include tetracarboxylic acid, hexacarboxylic acid, and octacarboxylic acid; examples of amine compounds that become polyamine residues include diamine, triamine, and tetraamine.

[0137] Y having the above structure (a) 1 Y 3 and Y 5The residues are derived from diamines, triamines, or their derivatives having structure (a). Furthermore, by using an amine compound corresponding to the polyamine residues during polymerization, these polyamine residues can be incorporated into the structural unit. From the viewpoint of the reliability of the obtained cured film, residues of the polyamine represented by formula (7) are preferred as residues of the polyamine having structure (a), and residues of the diamine represented by formula (8) that do not contain double bonds are more preferred. From the viewpoint of the economy of diamines and the elongation of the obtained cured film, residues of the diamine represented by formula (9) are particularly preferred.

[0138] [Chemical Formula 25]

[0139]

[0140] In equation (7), l represents any integer from 4 to 8, W independently represents any one of the structural units represented by equations (7a), (7b) or (7c), among l W, there are more than 2 structural units of (7c), the sum of the number of (7b) and (7c) is more than 4 and less than 8, and m and n independently represent any integer from 3 to 11.

[0141] [Chemical Formula 26]

[0142]

[0143] In general formula (8), e', f', g', and h' are natural numbers, e'+f' = 6 to 17, and g'+h' = 8 to 19. The dashed part refers to carbon-carbon single bonds or carbon-carbon double bonds. Among them, at least one in one molecule represents a double bond.

[0144] For specific examples of polyamines having structure (a), commercially available products such as dimeric diamines and melamines include "Versamine (registered trademark)" 551, "Versamine (registered trademark)" 552 (the above are trade names (manufactured by BASF Corporation)), "Priamine (registered trademark)" 1071, "Priamine (registered trademark)" 1073, "Priamine (registered trademark)" 1074, and "Priamine (registered trademark)" 1075 (the above are trade names (manufactured by Croda Japan Corporation)). Here, "Versamine (registered trademark)" 551 and "Priamine (registered trademark)" 1074 are dimeric diamine compounds that include the compound represented by formula (10), and "Versamine (registered trademark)" 552, "Priamine (registered trademark)" 1073, and "Priamine (registered trademark)" 1075 are dimeric diamine compounds that include the compound represented by formula (9). "Priamine (registered trademark) 1071" is a mixture of dimeric diamine and melamine.

[0145] X having the above structure (a) 1 X 3 and X 5 Residues derived from polycarboxylic acid residues or derivatives thereof having structure (a). Furthermore, by using an acid component corresponding to the polycarboxylic acid residue during polymerization, these acid residues can be incorporated into the structural unit. Examples of polycarboxylic acid residues having structure (a) include the aforementioned Y having structure (a). 1 Y 3 and Y 5 The examples include residues of polyamines reacting with trimellitic anhydride acyl chloride. More specifically, residues of formula (11) can be cited.

[0146] By using R in the above equation (2) 1 and R 2 R of equation (4) 3 and R 4 R of equation (6) 7 and R 8 The presence of olefinic unsaturated bonds at any position in the resin can impart an increase in heat resistance during curing due to the cross-linking of the resins.

[0147] As a method for introducing olefinic unsaturated bonds into a resin, known methods include: reacting hydroxyl and / or carboxyl groups in the resin with a compound having olefinic unsaturated double bond groups; polymerizing a resin using a monomer having olefinic unsaturated bonds; etc. From a reactivity point of view, electrophilic compounds having olefinic unsaturated double bond groups are preferred as compounds having olefinic unsaturated double bond groups.

[0148] Examples of electrophilic compounds include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thionone compounds, acetate compounds, carboxyl chlorides, carboxylic anhydrides, carboxylic acid reactive ester compounds, carboxylic acid compounds, haloalkyl compounds, azidoalkyl compounds, trifluoromethanesulfonate alkyl compounds, methanesulfonate alkyl compounds, toluenesulfonate alkyl compounds, or cyanide alkyl compounds. From the viewpoint of reactivity and the usability of the compound, isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds, or carboxylic anhydrides are preferred, and isocyanate compounds, epoxy compounds, and carboxylic anhydrides are more preferred.

[0149] To prevent cross-linking of the olefinic unsaturated bond sites during the reaction, a small amount of polymerization inhibitor may be used. Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, tert-butylcatechol, and bis-tert-butylhydroxytoluene. The amount of polymerization inhibitor added is preferably 0.1 mol% to 5 mol% of phenolic hydroxyl groups relative to the olefinic unsaturated bond of the alcohol.

[0150] In addition, from the perspective of improving exposure sensitivity, the preferred option is...

[0151] When the resin (A3) contains the structural unit represented by the above formula (2), there are multiple R... 1 and R 2 At least one of them is a group represented by formula (12) or formula (13),

[0152] When the resin (A3) contains the structural unit represented by the above formula (4), there are multiple R... 3 and R 4 At least one of them is a group represented by formula (12) or formula (13),

[0153] When the resin (A3) contains the structural unit represented by the above formula (6), there are multiple R... 7 and R 8 At least one of them is a group represented by formula (12) or formula (13).

[0154] [Chemical Formula 27]

[0155]

[0156] In equation (12), R 9 R represents the bonding group represented by -OCH2CH(OH)-, -OCONH-, -NHCH2CH(OH)-, or -NHCONH-. 10 R 11 and R 12 Each represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group, a represents an integer from 1 to 10, and * represents a bonding point.

[0157] Considering the ease with which groups are introduced into the resin (A3), R 9 Preferred options are -OCONH- and -NHCONH-.

[0158] [Chemical Formula 28]

[0159]

[0160] In general formula (13), R 13 R represents the bonding group represented by -OCO- or -NHCO-. 14 R 15 and R 16 Each represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group; b represents an integer from 0 to 10; and * represents a bonding point.

[0161] From the perspective of the heat resistance of the cured film, R 13 Preferred -NHCO-.

[0162] Relative to 100 mol% of all structural units of resin (A3), it is preferable to include 1 to 30 mol% of one or more resins selected from the group consisting of structural units represented by formulas (1), (3) and (5), more preferably 1 to 15 mol%. Within the above range, heat resistance can be improved while maintaining a low dielectric constant and a low dielectric loss tangent.

[0163] In the above formulas (1) to (6), X is preferred. 1 ~X 6 Comprising residues selected from the group consisting of residues chosen from the bisphenol A backbone, biphenyl backbone, hexafluoroisopropylidene backbone, and anhydride represented by formula (14), or Y 1 ~Y 6 It comprises any one or more residues selected from the group consisting of the bisphenol A backbone, the biphenyl backbone, the hexafluoroisopropylidene backbone and the diamine represented by formula (15).

[0164] By incorporating these structural units, it is possible to maintain a low dielectric constant and a low dielectric loss tangent while imparting heat resistance and solubility in organic solvents.

[0165] [Chemical Formula 29]

[0166]

[0167] In equation (14), z represents an integer from 6 to 20, and * represents a bond point.

[0168] [Chemical Formula 30]

[0169] H2N-Y 7 -NH2 (15)

[0170]

[0171] In equation (15), * represents the bonding point.

[0172] Examples of carboxylic acid compounds having residues of anhydrides represented by a bisphenol A backbone, a biphenyl backbone, or a hexafluoroisopropylidene backbone include 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic acid), 4,4'-(4,4'-isopropylidenediphenoxycarbonyl)bis(phthalic acid), and their derivatives. Among these, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic acid) are preferred from the viewpoint of solubility in organic solvents, transparency, and low dielectric constant.

[0173] Examples of amine compounds having residues representing diamines with a bisphenol A backbone, a biphenyl backbone, or a hexafluoroisopropylidene backbone include 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, bis(3- Amino-4-hydroxy)biphenyl, 4,4'-diamino-6,6'-bis(trifluoromethyl)-[1,1'-biphenyl]-3,3'-diol, bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and their derivatives.

[0174] Among these, from the viewpoint of solubility in organic solvents, transparency, and low dielectric constant, aromatic diamines such as 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane, as well as 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, and 1,3-bis(aminomethyl)cyclohexane of general formula (15) are preferred.

[0175] In the above equations (1) to (6), Y is further preferred. 1 ~Y 6 It includes the residues of the diamine represented by formula (16).

[0176] By including residues of these diamines, it is possible to further exhibit low dielectric loss tangent and impart heat resistance.

[0177] [Chemical Formula 31]

[0178]

[0179] In equation (16), R 17 and R 18 Each group independently represents a group selected from methyl, trifluoromethyl, or hydroxyl, and v and w represent integers from 0 to 4.

[0180] Examples of amine compounds containing these diamine residues include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-dimethylbiphenyl-4,4'-diamine, and 3,3'-dihydroxybenzidine.

[0181] As to become X 1 ~X 6 and X 8 ~X 10 Other usable carboxylic acid compounds with acid residues include, for example, benzopyrene, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)sulfide, and bis(3,4-dicarboxyphenyl)thioether. (3,4-Dicarboxyphenyl) ether, 1,3-bis(3,4-dicarboxyphenoxy)benzene, trimellitic acid (3,4-dicarboxyphenyl), 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, or 3,4,9,10-perylenetetracarboxylic acid, etc., are aromatic tetracarboxylic acids, or bicyclic [3.1.1.]hept-2-enetetracarboxylic acid, bicyclic [2.2.2.]octanetetracarboxylic acid, or adamantanetetracarboxylic acid, etc., are aliphatic tetracarboxylic acids.

[0182] These acids can be used directly, or as anhydrides, acyl chlorides, or active esters. Examples of active ester groups include, but are not limited to, the following structures.

[0183] [Chemical Formula 32]

[0184]

[0185] In the formula, A and D represent hydrogen atom, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, halogen, phenoxy, and nitro. * indicates a bonding site.

[0186] Furthermore, by using silicon-containing tetracarboxylic acids such as dimethylsilane phthalic acid or 1,3-bis(phthalic acid)tetramethyldisiloxane, adhesion to substrates and resistance to oxygen plasma and UV ozone treatment used in washing processes can be improved. These silicon-containing tetracarboxylic acids are preferably used at 1 mol% to 30 mol% of the total acid composition.

[0187] As a result of becoming Y 1 ~Y 6 and Y 8 ~Y 10Other amine compounds with amine residues that can be used, such as aromatic diamines, include m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenoxy)phenylbis(3-amino-4-hydroxyphenyl) ether, 3,4'-diaminodiphenylmethane, bis(3-amino-4-hydroxyphenyl)methylene, 4,4'-diaminodiphenylmethane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-aminophenoxyphenyl) sulfone, bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl) The list includes, but is not limited to, aromatic diamines such as fluorene, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, and others, as well as compounds in which a portion of the hydrogen atoms of their aromatic rings are replaced by alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, etc.

[0188] Examples of aliphatic diamines include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Examples of diamines having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane, which are preferred because they can improve adhesion to the substrate.

[0189] The aforementioned diamine compounds can be used directly or as compounds formed by isocyanate or trimethylsilyl alkylation of the amine site. Alternatively, two or more of these diamine compounds can be used in combination.

[0190] Furthermore, it is preferable that the structure of resin (A1), resin (A2), or resin (A3) contains a fluorine component. The presence of a fluorine component means that the structure contains an organic group with a fluorine atom, preferably X. 1 ~X 6 and X 8 ~X 10 , or Y 1 ~Y 6 and Y 8 ~Y 10Any of them contains an organic group having a fluorine atom. Known methods for introducing fluorine components include: methods for obtaining a resin by polymerization using a monomer having a fluorine atom; methods for reacting hydroxyl and / or carboxyl groups in the resin with a compound having a fluorine atom; etc.

[0191] Specifically, examples of compounds containing fluorine atoms include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides or compounds formed by replacing their aromatic rings with alkyl or halogen atoms, aromatic acid dianhydrides such as acid dianhydrides containing amide groups, aromatic diamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and compounds formed by replacing some hydrogen atoms of their aromatic rings with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, or halogen atoms.

[0192] Fluorine, due to its large atomic radius, has the effect of increasing free volume, thus reducing the relative permittivity and dielectric loss tangent. The organic groups containing fluorine atoms are preferably 30 mol% or more relative to 100 mol% of all structural units of resin (A1), resin (A2), or resin (A3). Furthermore, to obtain good adhesion to the substrate, the organic groups containing fluorine atoms are preferably 90 mol% or less.

[0193] Furthermore, it is preferable that the resin (A1), resin (A2), or resin (A3) has 1 to 25 mol% phenolic hydroxyl groups relative to 100 mol% of all structural units. Preferably, X 1 ~X 6 and X 8 ~X 10 , or Y 1 ~Y 6 and Y 8 ~Y 10 Any one of them is an organic group having a phenolic hydroxyl group. Phenolic hydroxyl groups can result in improved heat resistance due to hydrogen bonding interactions, high mechanical properties due to the contribution of the reaction with the crosslinking agent, and chemical resistance. If the phenolic hydroxyl group is a polar group, there is a tendency for a worse dielectric loss tangent; however, if it is 1 to 25 mol% relative to 100 mol% of all structural units of resin (A1), resin (A2), or resin (A3), mechanical properties and chemical resistance can be improved without a worsening of the dielectric loss tangent. More preferably, it is 1 to 15 mol%.

[0194] Specifically, examples of compounds having phenolic hydroxyl groups include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or compounds in which their aromatic rings are substituted with alkyl or halogen atoms; aromatic acid dianhydrides such as acid dianhydrides having amide groups; bis(3-amino-4-hydroxyphenyl)hexafluoropropane; bis(3-amino-4-hydroxyphenyl) sulfone; bis(3-amino-4-hydroxyphenyl)propane; bis(3-amino-4-hydroxyphenyl)methylene; bis(3-amino-4-hydroxyphenyl) ether; bis(3-amino-4-hydroxy)biphenyl; bis(3-amino-4-hydroxyphenyl)fluorene and other hydroxyl-containing diamines; and compounds in which some hydrogen atoms of their aromatic rings are substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, etc.

[0195] Furthermore, in order to improve the storage stability of the photosensitive resin composition of the present invention and to enable it to perform various functions, the ends of the main chain of components (A1) to (A3) can be capped with a capping agent. Examples of capping agents include monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds. In addition, by using a capping agent having hydroxyl, carboxyl, sulfonic acid, thiol, vinyl, ethynyl, maleimide, or allyl groups to cap the ends of the resin, the exposure sensitivity, the mechanical properties of the resulting cured film, etc., can be easily adjusted to an optimal range.

[0196] From the viewpoint of solubility in the developer and the mechanical properties of the resulting cured film, the proportion of the capping agent introduced is preferably 0.1 mol% to 60 mol%, and particularly preferably 5 mol% to 50 mol%. This allows for the reaction of various capping agents to introduce a variety of different terminal groups.

[0197] The monoamine used as the capping agent can be a known compound, preferably aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 1-hydroxy-7-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 3-aminobenzoic acid, 3-aminophenol, 3-aminothiophenol, etc. Two or more of these can also be used.

[0198] As anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds, known compounds can be used, but phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, itaconic anhydride, etc., are preferred. Maleic anhydride and itaconic anhydride are particularly preferred. Two or more of these can be used.

[0199] In this invention, the weight-average molecular weight of components (A1) to (A3) is preferably 5,000 to 100,000. By using GPC (gel permeation chromatography) and estimating the weight-average molecular weight as that of polystyrene, a weight-average molecular weight of 5,000 or higher can be achieved, improving mechanical properties such as elongation at break and elastic modulus after curing. On the other hand, by using a weight-average molecular weight of 100,000 or lower, developability can be improved. For obtaining mechanical properties, a weight-average molecular weight of 10,000 or higher is more preferable. Furthermore, in the case of a resin containing two or more of components (A1) to (A3), it is sufficient that at least one of them has a weight-average molecular weight within the above-mentioned range.

[0200] The photosensitive resin composition of the present invention contains a (B) photopolymerization initiator. By containing the (B) photopolymerization initiator, patterning can be performed via exposure and development processes. The (B) photopolymerization initiator is not particularly limited to any compound that generates free radicals through exposure; alkyl benzophenone compounds, aminobenzophenone compounds, diketone compounds, ketone ester compounds, phosphine oxide compounds, oxime ester compounds, and benzoate ester compounds are preferred due to their excellent sensitivity, stability, and ease of synthesis. From the viewpoint of sensitivity, alkyl benzophenone compounds and oxime ester compounds are preferred, and oxime ester compounds are particularly preferred. Furthermore, when processing thick films with a thickness of 5 μm or more, from the viewpoint of resolution, phosphine oxide compounds are preferred.

[0201] Examples of alkyl phenyl ketone compounds include, for instance, α-aminoalkyl phenyl ketone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one, α-hydroxyalkyl phenyl ketone compounds such as 1-hydroxycyclohexylphenyl ketone and benzoin, α-alkoxyalkyl phenyl ketone compounds such as 4-benzoyl-4-methylphenyl ketone and 2,3-diethoxyacetophenone. Among these, α-aminoalkyl phenyl ketone compounds are preferred due to their high sensitivity.

[0202] Examples of phosphine oxide compounds include, for instance, 6-trimethylbenzoylphenylphosphine oxide.

[0203] Examples of oxime ester compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], NCI-831, NCI-930 (all trade names, manufactured by ADEKA Co., Ltd.), and "Irgacure (registered trademark)" OXE-03, OXE-04 (all trade names, manufactured by BASF Co., Ltd.).

[0204] Examples of aminobenzophenone compounds include 4,4-bis(dimethylamino)benzophenone. Examples of diketone compounds include benzoyl. Examples of ketone ester compounds include methyl benzoylformate. Examples of benzoic acid ester compounds include methyl o-benzoylbenzoate and ethyl p-dimethylaminobenzoate.

[0205] Other specific examples of photopolymerization initiators (B) include benzophenone, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanth-2-yloxy)-N,N,N-trimethyl-1-propanediamine chloride, anthraquinone, triphenylphosphine, carbon tetrabromide, etc.

[0206] When the total amount of components (A1) to (A3) and any compounds having two or more olefinic unsaturated bonds is set to 100 parts by mass, the content of the photopolymerization initiator is preferably 0.5 to 20 parts by mass. This is because it provides sufficient sensitivity and suppresses degassing during thermosetting. More preferably, it is 1.0 to 10 parts by mass.

[0207] The photosensitive resin composition of the present invention may contain a sensitizer to enhance the function of the (B) photopolymerization initiator. By containing a sensitizer, sensitivity can be improved and the photosensitive wavelength can be adjusted. Examples of sensitizers include, but are not limited to, bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine, and their derivatives.

[0208] The photosensitive resin composition of the present invention preferably further contains a compound (C) having two or more olefinic unsaturated bonds and an alicyclic structure (hereinafter sometimes simply referred to as "(C) component"). By containing the (C) component, the exposure sensitivity is further improved due to the increased crosslinking density during exposure, which helps to reduce exposure amount and developing film loss. As the (C) component, a known alicyclic (meth)acrylate compound may be contained, which can simultaneously possess low dielectric constant, low dielectric loss tangent, and exposure sensitivity at a high level.

[0209] Examples of polyfunctional (meth)acrylates containing alicyclic structures include dihydroxymethyl-tricyclodecane di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, 1,4-cyclohexanediethanol di(meth)acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate, and EO-modified hydrogenated bisphenol A di(meth)acrylate.

[0210] The content of component (C) is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of components (A1) to (A3). Within the above range, it is easy to obtain the effect of improving exposure sensitivity, low dielectric constant, and low dielectric loss tangent.

[0211] In addition to component (C), the photosensitive resin composition of the present invention may also contain known (meth)acrylate compounds.

[0212] Examples of polyfunctional (meth)acrylates include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene.

[0213] Other polyfunctional (meth)acrylate compounds include, for example, epoxy (meth)acrylates obtained by reacting polyfunctional epoxy compounds with (meth)acrylic acid. Epoxy (meth)acrylates, due to their hydrophilicity, can be used to improve alkaline developability. These polyfunctional epoxy compounds are preferred due to their excellent heat resistance and chemical resistance.

[0214] [Chemical Formula 33]

[0215]

[0216] The photosensitive resin composition of the present invention preferably contains a thermal crosslinking agent (D) (hereinafter sometimes simply referred to as "(D) component"). By containing the (D) component, the heat resistance and chemical resistance of the cured film can be improved.

[0217] Examples of thermal crosslinking agents include compounds with epoxy structures, compounds with hydroxymethyl structures, and compounds with alkoxymethyl structures.

[0218] Compounds having an epoxy structure may include known compounds. Examples include "Epiclon (registered trademark)" 850-S, "Epiclon (registered trademark)" HP-4032, "Epiclon (registered trademark)" HP-7200 (these are trade names, available from Dai Nippon Ink Chemical Industry Co., Ltd.), "Rika Resin (registered trademark)" BPO-20E, "Rika Resin (registered trademark)" BEO-60E (these are trade names, available from Shin Nippon Rika Co., Ltd.), EP-4003S, and EP-4000S (these are trade names, available from ADEKA Co., Ltd.), but are not limited to these.

[0219] Compounds having a hydroxymethyl structure and compounds having an alkoxymethyl structure may also include known compounds. Examples include DML-PC, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, available from Honshu Chemical Industry Co., Ltd.), "NIKALAC (registered trademark)" MX-290, "NIKALAC (registered trademark)" MX-280, "NIKALAC (registered trademark)" MX-270, "NIKALAC (registered trademark)" MX-279, "NIKALAC (registered trademark)" MW-100LM, and "NIKALAC (registered trademark)" MX-750LM (trade names, available from Sanwa Chemical Co., Ltd.).

[0220] Among these compounds, from the viewpoints of heat resistance and chemical resistance of the cured film and storage stability, compounds selected from any one of TMOM-BPAP, NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM are preferred.

[0221] The amount of thermal crosslinking agent added is preferably 1 to 20.0 parts by mass, more preferably 5 to 15 parts by mass, relative to 100 parts by mass of components (A1) to (A3). Within the above range, the chemical resistance and heat resistance of the cured film can be improved while maintaining a low dielectric loss tangent.

[0222] The photosensitive resin composition of the present invention may contain an antioxidant. By containing an antioxidant, yellowing of the cured film and a decrease in mechanical properties such as elongation during subsequent heat treatment processes can be suppressed. Furthermore, the antioxidant is preferred because it inhibits the oxidation of metal materials by providing rust prevention.

[0223] As antioxidants, hindered phenolic antioxidants or hindered amine antioxidants are preferred.

[0224] Examples of hindered phenolic antioxidants include, but are not limited to, Irganox (registered trademark) 245, 3114, 1010, 1098, 1135, 259, and 035 (trade names, manufactured by BASF Corporation) or 2,6-bis(tert-butyl)-p-cresol.

[0225] Examples of hindered amine antioxidants include "TINUVIN (registered trademark)" 144, 292, 765, and 123 (these are trade names, manufactured by BASF Corporation).

[0226] Other antioxidants include phenol, catechol, resorcinol, hydroquinone, 4-tert-butylcatechol, 2,6-bis(tert-butyl)-p-cresol, phenothiazine, and 4-methoxyphenol. The amount of antioxidant added is preferably 0.1 to 10.0 parts by weight, more preferably 0.3 to 5.0 parts by weight, relative to 100 parts by weight of components (A1) to (A3). Within the above range, it is possible to adequately maintain developability and inhibit discoloration caused by heat treatment.

[0227] The photosensitive resin composition of the present invention can contain nitrogen-containing heterocyclic compounds. High adhesion can be achieved on substrates of easily oxidized metals such as copper, aluminum, and silver using nitrogen-containing heterocyclic compounds. The mechanism is not yet clear, but it is speculated that the interaction with the metal surface is due to the metal coordination ability of the nitrogen atom, and the interaction is stabilized by the swelling of the heterocycle.

[0228] Examples of nitrogen-containing heterocyclic compounds include imidazole, pyrazole, indazole, carbazole, pyrazoline, pyrazolidine, triazole, tetraazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and their derivatives.

[0229] As nitrogen-containing heterocyclic compounds, from the viewpoint of reactivity with metals, 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole are preferred.

[0230] The amount of nitrogen-containing heterocyclic compound added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, more preferably 0.05 parts by mass or more and 3.0 parts by mass or less, relative to 100 parts by mass of components (A1) to (A3). Within the above range, the developability and the stabilization effect of the substrate metal can be adequately maintained.

[0231] The photosensitive resin composition of the present invention may contain a solvent. Examples of solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N'-dimethylpropylene urea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionic acid amide; ethers such as tetrahydrofuran, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as methyl ethyl ketone, diisobutyl ketone, and cyclohexanone; esters such as butyl acetate and propylene glycol monomethyl ether acetate; alcohols such as ethyl lactate and methyl lactate; diacetone alcohol and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more of these solvents may be present.

[0232] Regarding the content of the solvent, in order to dissolve the composition, it is preferable to contain 100 parts by mass or more relative to 100 parts by mass of components (A1) to (A3), and in order to form a coating film with a thickness of 1 μm or more, it is preferable to contain 1,500 parts by mass or less.

[0233] Furthermore, to improve adhesion to the substrate, a silane coupling agent as a silicon component can be included in the photosensitive resin composition of the present invention, within a range that does not impair storage stability. Examples of silane coupling agents include trimethoxyaminopropylsilane, trimethoxycyclohexylepoxyethylsilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, trimethoxyglycidyloxypropylsilane, tris(trimethoxysilylpropyl)isocyanurate, triethoxyaminopropylsilane, and a reaction product of trimethoxyaminopropylsilane and anhydride. This reaction product can be used in an amide acid state or an imidized state. Examples of acid anhydrides that can be used in the reaction include succinic anhydride, maleic anhydride, nadicanhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-benzophenone tetracarboxylic anhydride, and 4,4'-oxophthalic dianhydride. The preferred content of the silane coupling agent is 0.01 to 10 parts by mass relative to 100 parts by mass of components (A1) to (A3).

[0234] The following describes a photosensitive sheet formed on a substrate using the photosensitive resin composition of the present invention.

[0235] The photosensitive sheet of the present invention refers to an incompletely cured sheet material obtained by coating the photosensitive resin composition of the present invention onto a substrate and drying it at a temperature and time within a range that allows the solvent to evaporate. It refers to a material that is soluble in organic solvents or alkaline aqueous solutions.

[0236] There are no particular limitations on the substrate; various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. For the bonding surface between the substrate and the photosensitive resin composition, surface treatments such as silicone, silane coupling agents, aluminum chelating agents, and polyurea can be applied to improve adhesion and peelability. Furthermore, there are no particular limitations on the thickness of the substrate; from a workability perspective, a range of 10 to 100 μm is preferred. Moreover, a protective film can be applied to the film surface to protect the surface of the coated photosensitive composition. This protects the surface of the photosensitive resin composition from pollutants such as atmospheric debris and dust.

[0237] Methods for coating a photosensitive resin composition onto a substrate include spin coating, spray coating, roller coating, screen printing, doctor blade coating, die coating, calender coating, meniscus coating, bar coating, roller coating, comma roller coating, gravure coating, screen coating, and slit coating. Furthermore, the coating film thickness varies depending on the coating method, the concentration of solid components in the composition, viscosity, etc. Generally, from the viewpoint of coating film uniformity, the dried film thickness is preferably 0.5 μm to 100 μm or less.

[0238] For drying, ovens, heating plates, infrared radiation, etc., can be used. The drying temperature and time only need to be within the range that allows the solvent to evaporate, preferably set appropriately to the range where the photosensitive resin composition is in an uncured or semi-cured state. Specifically, drying is preferably carried out in the range of 40°C to 150°C for 1 minute to several tens of minutes. In addition, these temperatures can be combined and raised in stages, for example, heat treatment can be performed at 80°C and 90°C for 2 minutes each.

[0239] The cured film formed by curing the photosensitive resin composition or photosensitive sheet of the present invention will now be described.

[0240] The cured film of the present invention can be obtained by heat treatment of a photosensitive resin composition or a photosensitive sheet. The heat treatment temperature can be anywhere from 150°C to 350°C. For example, the process can be performed for 5 minutes to 5 hours while simultaneously increasing the temperature in stages or continuously within a certain temperature range. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. The lower limit of the curing conditions in the present invention is preferably 170°C or higher, and more preferably 180°C or higher for sufficient curing. Furthermore, there is no particular limitation on the upper limit of the curing conditions; from the viewpoint of suppressing film shrinkage and stress, it is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 230°C or lower.

[0241] The following describes a method for forming an embossed pattern of a cured film using the photosensitive resin composition or photosensitive sheet of the present invention.

[0242] The photosensitive resin composition of the present invention is coated onto a substrate, or the aforementioned photosensitive sheet is laminated onto a substrate. As the substrate, a substrate plated with metallic copper or a silicon wafer can be used; additionally, as the material, ceramics, gallium arsenide, etc., can be used, but are not limited to these. As the coating method, methods such as spin coating, spray coating, and roller coating using a spin coater are available. Furthermore, the coating film thickness varies depending on the coating method, the concentration of solid components in the composition, viscosity, etc., and is generally applied in a manner that results in a film thickness of 0.1 to 150 μm after drying.

[0243] To improve the adhesion between the substrate and the photosensitive resin composition, the substrate can be pretreated with the aforementioned silane coupling agent. For example, a solution containing 0.5–20% by mass of the silane coupling agent is prepared in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Next, the substrate is surface-treated with the prepared solution by spin coating, dipping, spraying, or steam treatment. Depending on the application, a heat treatment at 50°C to 300°C is then performed to allow the substrate to react with the silane coupling agent.

[0244] Next, the substrate coated with the photosensitive resin composition or laminated with the photosensitive sheet of the present invention is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, heating plate, infrared radiation, etc., at a temperature ranging from 50°C to 150°C for 1 minute to several hours. It should be noted that in the case of photosensitive sheets, a drying process is not always necessary.

[0245] Next, the photosensitive resin composition film is exposed. At this time, chemical rays can be irradiated through a mask having the desired pattern to perform exposure. Chemical rays used for exposure include ultraviolet light, visible light, electron beams, X-rays, etc. In this invention, the i-line (365nm), h-line (405nm), and g-line (436nm) of a mercury lamp are preferably used.

[0246] Next, as needed, the exposed photosensitive resin composition film can be subjected to a post-exposure baking (PEB) process. The PEB process preferably uses an oven, heating plate, infrared radiation, etc., and is carried out at a temperature of 50°C to 150°C for 1 minute to several hours.

[0247] Next, the exposed photosensitive resin film is developed. To form a resin pattern, unexposed areas are removed using a developer after exposure. The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of a good solvent and a poor solvent. For example, good solvents include N-methylpyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, and γ-butyrolactone. Poor solvents include toluene, xylene, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, the ratio of the poor solvent to the good solvent is preferably adjusted according to the solubility of the polymer in the photosensitive resin composition. Alternatively, two or more solvents (e.g., several) can be used in combination.

[0248] Furthermore, alkaline aqueous solution development can be performed when the photosensitive resin composition is dissolved in an alkaline aqueous solution. The developing solution used in development is one that dissolves and removes the polymer soluble in the alkaline aqueous solution; typically, it is an alkaline aqueous solution containing an alkaline compound. Examples of alkaline compounds include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Depending on the circumstances, these alkaline aqueous solutions may also contain one or a combination of polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, and isobutyl ketone.

[0249] Preferably, rinsing is performed after development using an organic solvent or water. When using an organic solvent, in addition to the aforementioned developer, examples include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When using water, alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate can be added to the water for rinsing.

[0250] Next, the developed photosensitive resin film is subjected to heat treatment. After development, a temperature of 150°C to 350°C is applied to induce a thermal crosslinking reaction, thereby curing the film. This heat treatment is performed for 5 minutes to 5 hours, either by gradually increasing the temperature at a selected temperature or by continuously increasing the temperature within a selected temperature range. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. The lower limit of the curing conditions in this invention is preferably 170°C or higher, and more preferably 180°C or higher for sufficient curing. Furthermore, there is no particular limitation on the upper limit of the curing conditions, but from the viewpoint of suppressing film shrinkage and stress, it is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 230°C or lower.

[0251] The electronic component or display device of the present invention includes the cured film of the present invention. Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components such as resistors, capacitors, and inductors.

[0252] In addition, electronic components also include hermetically sealed packages designed to improve the durability of these components, and modules that integrate multiple components. Furthermore, electronic components that use semiconductors are also called semiconductor devices or semiconductor packages. Examples of semiconductor devices include display panels and touch sensor panels.

[0253] As a specific example of a cured film used in electronic components or display devices, it can be appropriately used as a passivation film for semiconductors, a surface protective film for semiconductor elements, TFTs (Thin Film Transistors), an interlayer insulating film between rewiring layers in multilayer wiring for high-density mounting of 2 to 10 layers, an insulating film and protective film for touch panel displays, an insulating film for organic electroluminescence (EL) elements, a planarization film for TFT substrates used in display devices employing organic EL elements, an on-chip microlens for solid-state imaging elements, and a planarization film for various displays and solid-state imaging elements, etc., but is not limited to these applications, and can be used in various structures. Among these, it is preferred to use it as an interlayer insulating film in multilayer wiring for high-density mounting.

[0254] Hereinafter, an application example of using a cured film formed by curing the photosensitive resin composition of the present invention in a semiconductor device having bumps will be described with reference to the accompanying drawings. Figure 1 This is an enlarged cross-sectional view of the pad portion of the bumped semiconductor device in this invention. (See image below.) Figure 1As shown, on the silicon wafer 1, a passivation film 3 is formed on the aluminum (hereinafter referred to as Al) pads 2 for input / output, and via holes are formed on the passivation film 3. An insulating film 4 is formed thereon as a pattern formed by curing the photosensitive resin composition of the present invention. A metal (Cr, Ti, etc.) film 5 is then formed in a manner connected to the Al pads 2, and metal wiring (Al, Cu, etc.) 6 is formed by electroplating or the like. For the metal film 5, the periphery of the solder bumps 10 is etched to insulate the pads from each other. A barrier metal 8 and solder bumps 10 are formed on the insulating pads. The curing film formed by curing the photosensitive resin composition of the insulating film 7 can be thickened in the scribing 9.

[0255] under, Figure 2 It records detailed methods for manufacturing semiconductor devices. For example... Figure 2 As shown in 2a, on the silicon wafer 1, a passivation film 3 is further formed on the input / output Al pads 2, and an insulating film 4 is formed as a pattern formed from a cured film obtained by curing the photosensitive resin composition of the present invention. Next, as... Figure 2 As shown in 2b, a metal (Cr, Ti, etc.) film 5 is formed in a manner connected to the Al pad 2, as shown in 2b. Figure 2 As shown in 2c, the metal wiring 6 is formed using a plating method. Next, as... Figure 2 As shown in 2d', the photosensitive resin composition of the present invention before curing is coated, and an insulating film 7 is formed by a photolithography process. Figure 2 The pattern shown in 2d. At this time, the photosensitive resin composition of the insulating film 7 before curing is processed into a thick film in the scribing 9. In the case of forming a multilayer wiring structure with 3 or more layers, the above process can be repeated to form each layer.

[0256] Next, as Figure 2 As shown in 2e and 2f, a barrier metal 8 and solder bumps 10 are formed. Then, each chip is cut along the final scribing line 9. If the insulating film 7 is not patterned in the scribing line 9 or if residue remains, cracks may occur during cutting, affecting the chip's reliability evaluation. Therefore, to obtain high reliability for semiconductor devices, the patterning technique of this invention, which provides excellent patterning capabilities in thick film processing, is highly preferred.

[0257] The antenna element of the present invention is preferably an antenna element having at least one antenna wiring and the cured film of the present invention. The antenna wiring includes at least one selected from the group consisting of a zigzag loop antenna, a coil loop antenna, a zigzag monopole antenna, a zigzag dipole antenna, and a microstrip antenna, and each antenna portion in the antenna wiring has a proprietary area of ​​1000 mm². 2 The cured film is described below as an insulating film that insulates the ground wire from the antenna wiring.

[0258] Here, antenna elements refer to electronic components that utilize resistors, inductors, and capacitors as passive elements and possess radio wave transmission and reception capabilities. There are no particular restrictions on the materials used in antenna wiring, as long as they are conductive; examples include metals such as copper, gold, silver, platinum, aluminum, molybdenum, and titanium. These can be laminates or alloys of different metals, or composites with organic materials such as polymers. Additionally, carbon materials such as graphite, graphene, and carbon nanotubes, as well as conductive polymers, can also be used. Among these, copper is preferred due to its excellent cost, conductivity, and stability.

[0259] For the antenna element of the present invention, in specific use Figure 3 Please provide an explanation. Figure 3 This is a schematic diagram of a coplanar powered microstrip antenna, a type of planar antenna. 1a shows a cross-sectional view, and 1b shows a top view. First, the formation method will be described. The photosensitive resin composition of the present invention is coated onto a copper foil and pre-baked, or an uncured photosensitive sheet is laminated onto the copper foil. Next, the copper foil is laminated and thermally cured, thereby forming a cured film with copper foil on both sides. Then, by patterning using a subtractive method, a microstrip antenna with… Figure 3 The antenna element is an antenna with a copper wiring pattern of microstrip line (MSL).

[0260] Below, on Figure 3 The antenna pattern is explained below. In 1a, 15 represents the ground wire (full surface), and 16 represents the insulating film that forms the substrate of the antenna. The layers 11 to 13 above represent the cross-sections of the antenna wiring obtained through the above patterning. The thickness J of the ground wire wiring and the thickness K of the antenna wiring can be arbitrary depending on the impedance design, but are typically 2 to 20 μm. In 1b, 11 represents the antenna section, 12 represents the matching circuit, 13 represents the MSL power supply line, and 14 represents the power supply point. To achieve impedance matching between the antenna section 11 and the MSL power supply line 13, the length M of the matching circuit 12 has a length of 1 / 4λr (λr = (wavelength of the transmitted radio wave) / (dielectric constant of the insulating material)). 1 / 2 Furthermore, the width W and length L of the antenna section 11 are designed to be 1 / 2λr. The antenna section length L can also be set to 1 / 2λr or less depending on the impedance design. The cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, thus providing a high-efficiency, high-gain antenna element. Furthermore, considering these characteristics, the antenna element using the insulating film of the present invention is suitable as a high-frequency antenna, by making the area of ​​the antenna section (=L×W) 1000mm². 2 The following dimensions enable the formation of small antenna elements. Through the above methods, high-efficiency, high-gain, and compact high-frequency antenna elements can be obtained.

[0261] Furthermore, the semiconductor package of the present invention is preferably a semiconductor package comprising at least a semiconductor element, a redistribution layer, a sealing resin, and an antenna wiring, wherein the antenna wiring includes at least one selected from the group consisting of a zigzag loop antenna, a coil loop antenna, a zigzag monopole antenna, a zigzag dipole antenna, and a microstrip antenna, and the proprietary area of ​​each antenna portion in the antenna wiring is 1000 mm². 2 The insulating layer of the redistribution layer and / or the sealing resin thereunder contain the cured film of the present invention, the sealing resin being located between the ground wire and the antenna wiring.

[0262] The materials used in the antenna wiring can be those described in the above description of the antenna elements. Additionally, as semiconductor elements, examples include integrated circuits (RFICs) that process signals transmitted and received by the antenna, and semiconductor elements such as amplifiers and noise filters can also be included. From the viewpoint of cost and reliability, it is preferable that the metal wiring has 1 to 3 layers and the insulating layer has 1 to 4 layers as the redistribution layer, but this is not a limitation. The insulating layer is preferably the cured film of the present invention. As the sealing resin, the cured film of the present invention is preferred. When used in the insulating layer of the redistribution layer, there are no restrictions; any sealant can be used, typically a mixture of epoxy resin and inorganic filler.

[0263] This section describes a semiconductor package that includes an IC chip (semiconductor element), a redistribution layer, sealing resin, and antenna wiring. Figure 4This is a schematic diagram relating to a cross-section of a semiconductor package comprising an IC chip (semiconductor element), redistribution wiring, sealing resin, and antenna elements. A redistribution layer (2 layers of copper, 3 layers of insulating film) is formed on the electrode pads 202 of the IC chip 201, utilizing copper wiring 209 and an insulating film 210 formed from the curing film of the present invention. Barrier metal 211 and solder bumps 212 are formed on the pads of the redistribution layer (copper wiring 209 and insulating film 210). To seal the IC chip, a first sealing resin 208 composed of the curing film of the present invention is formed, and copper wiring 209 serving as a ground line for the antenna is further formed thereon. A first via wiring 207 connecting the ground line 206 to the redistribution layer (copper wiring 209 and insulating film 210) is formed through a via formed within the first sealing resin 208. A second sealing resin 205 composed of the curing film of the present invention is formed on the first sealing resin 208 and the ground line 206, and a planar antenna wiring 204 is formed thereon. A second through-hole wiring 203 is formed through through-holes formed within the first sealing resin 208 and the second sealing resin 205, connecting the planar antenna wiring 204 to the rewiring layer (copper wiring 209 and insulating film 210). The thickness of each insulating film 210 is preferably 10–20 μm, and the thicknesses of the first and second sealing resins are preferably 50–200 μm and 100–400 μm, respectively. The cured film of the present invention has a low dielectric constant and a low dielectric loss tangent; therefore, the semiconductor package containing the obtained antenna element is highly efficient, has high gain, and exhibits low transmission loss within the package.

[0264] Furthermore, for the antenna element of the present invention, it is preferable that the height of the antenna wiring is 50 to 200 μm and the thickness of the curing film is 80 to 300 μm, so that the antenna wiring and the curing film of the present invention are laminated together. By laminating the antenna wiring and the curing film and keeping the height of the antenna wiring and the thickness of the curing film within the above ranges, it is possible to transmit and receive signals in a small size over a wide range. The curing film of the present invention has a low dielectric constant and a low dielectric loss tangent, thus providing a high-efficiency, high-gain antenna element.

[0265] Example

[0266] Hereinafter, examples will be given to illustrate the present invention, but the present invention is not limited to these examples. First, the evaluation methods in each example and comparative example will be described. In the evaluation, the photosensitive resin composition (hereinafter referred to as varnish) that has been filtered before curing using a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore size of 1 μm was used.

[0267] (1) Molecular weight determination

[0268] The weight-average molecular weight (Mw) of components (A1) to (A3) was determined using a Waters 2690-996 GPC (Gel Permeation Chromatography) apparatus (manufactured by Japan Waters Corporation). The developing solvent was N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and the weight-average molecular weight (Mw) and dispersity (PDI = Mw / Mn) were calculated using polystyrene as the conversion factor.

[0269] (2) Pattern processing properties

[0270] (2)-1 Immunosorbency and Sensitivity

[0271] After spin coating the varnish onto the silicon wafer using a spin coater (Mikasa Co., Ltd. 1H-360S), a pre-baked film with a thickness of 11μm is produced by pre-baking at 120°C for 3 minutes using a heating plate (Dai Nippon Screen Manufacturing Co., Ltd. SCW-636). For the obtained pre-baked film, a parallel light mask aligner (hereinafter referred to as PLA) (Canon Corporation PLA-501F) was used, with an ultra-high pressure mercury lamp as the light source (a mixture of gamma rays, h rays, and i rays). A grayscale mask for sensitivity measurement (with a 1:1 pattern of lines and gaps of 2μm, 3μm, 4μm, 5μm, 6μm, 8μm, 10μm, 12.5μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, and 50μm) was used, with regions having transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and 60%, respectively) was used for contact measurement at 1000 mJ / cm². 2 The sample was then exposed to 120°C for 3 minutes and baked. Development was then performed using a coating and developing apparatus (Tokyo Electron MARK-7). Cyclopentanone (CP) was used for a 30-second spray development, followed by a 15-second rinse with propylene glycol monomethyl ether acetate (PGMEA). If over- or under-development occurred, the development and rinsing times were adjusted accordingly.

[0272] After development, the film thickness was measured. The minimum exposure value with a film thickness exceeding 95 when the film thickness of the 1000mJ exposure section was set to 100 was defined as the optimal exposure value. Furthermore, the residual film rate, obtained by dividing the film thickness at the optimal exposure value by the pre-baked film thickness, was measured. The sensitivity evaluation criteria are as follows.

[0273] A: The residual film rate is over 90%.

[0274] B: The residual film rate is above 80% and less than 90%.

[0275] C: The residual film rate is 70% or higher but less than 80%.

[0276] D: Residual film rate is 50% or higher but less than 70%.

[0277] E: Residual film rate less than 50%

[0278] In addition, the exposure was measured using an I-line illuminance meter. It should be noted that the film thickness was measured using a Lambda Ace STM-602 manufactured by Dai Nippon Screen Manufacturing Co., Ltd., with a refractive index of 1.629. The film thicknesses described below are also measured using the same method.

[0279] (2)-2 resolution

[0280] The minimum pattern size after development was determined at the optimal exposure defined in (2)-1.

[0281] (3) Determination of dielectric constant and dielectric loss tangent

[0282] With a film thickness of 11 μm after pre-baking at 120°C for 3 minutes, a MARK-7 coating and developing system was used to spin-coat a 6-inch silicon wafer and pre-baked. Then, PLA was used to coat the entire surface with 300 mJ / cm². 2 Exposure was performed using an inert oven (Koyo Thermo System Co., Ltd. CLH-21CD-S) at an oxygen concentration below 20 ppm, with the temperature increased to 220°C at a rate of 3.5°C / min, and the temperature was maintained at each temperature for 1 hour. The silicon wafer was removed when the temperature reached below 50°C and immersed in 45% hydrofluoric acid for 1 minute, thereby peeling off the cured film of the resin composition from the wafer. This film was cut into strips 1.5 cm wide and 3 cm long, and the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using the perturbation-mode cavity resonator method according to ASTM D2520 at room temperature of 23.0°C and humidity of 45.0% RH. The dielectric properties are shown in Table 1 below, measured in 5 grades.

[0283] [Table 1]

[0284] Table 1

[0285]

[0286] (4) Determination of the glass transition point of the cured film after curing

[0287] Similar to the above-mentioned "(3) Determination of dielectric constant and dielectric loss tangent", a self-supporting film for curing was prepared. The film was cut out with a single blade at a width of 0.5 cm and a length of 3.0 cm. Measurements were performed using a thermomechanical analyzer (Seiko Instruments, TMA / SS6100) under a nitrogen flow rate of 80 mL / min, with the temperature increased from 25 °C to 400 °C at a rate of 10 °C / min. The evaluation criteria are shown below. A higher glass transition temperature indicates higher heat resistance of the cured film.

[0288] A: The glass transition point is above 200℃.

[0289] B: The glass transition point is above 180℃ and below 200℃.

[0290] C: The glass transition point is above 150℃ and below 180℃.

[0291] D: The glass transition point is above 120℃ and below 150℃.

[0292] E: The glass transition point is below 120℃.

[0293] (5) Determination of the elongation at the breaking point of the cured film after curing

[0294] Similar to the above "(3) Determination of dielectric constant and dielectric loss tangent", a self-supporting film for curing was prepared. The film was cut into strips 1.5 cm wide and 9 cm long. Using a Tensilon RTM-100 (manufactured by Orientech Co., Ltd.), the strips were stretched at a stretching speed of 50 mm / min (clamping interval = 2 cm) at room temperature of 23.0°C and humidity of 45.0%RH, and the elongation at break (%) was measured. The measurement was performed on 10 strips for each sample, and the average of the top 5 values ​​was calculated (significant figures = 3 digits).

[0295] (6) Evaluation of chemical resistance

[0296] With a film thickness of 10 μm after pre-baking at 120°C for 3 minutes, a MARK-7 coating and developing system was used to coat a clear varnish onto a silicon wafer via spin coating and pre-baking. Then, a PLA coating was applied to the entire surface of the coated film at 300 mJ / cm². 2Exposure was performed using an inert oven (CLH-21CD-S) with a nitrogen flow and an oxygen concentration below 20 ppm, at a heating rate of 3.5 °C per minute to 230 °C, and then heat-treated at 230 °C for 1 hour. The silicon wafer was removed at a temperature below 50 °C, and the cured film was immersed in an organic chemical solution (dimethyl sulfoxide: 25% TMAH aqueous solution = 92:2) at 65 °C for 60 minutes, observing for pattern peeling and dissolution. The results were graded as follows: no pattern peeling and film thickness change less than 5% was rated A; no pattern peeling and film thickness change (indicating swelling or dissolution) exceeding 5% but less than 10% was rated B; no pattern peeling and film thickness change exceeding 10% but less than 20% was rated C; no pattern peeling and film thickness change exceeding 20% ​​but less than 30% was rated D; and pattern peeling with no film residue or film thickness change exceeding 30% was rated E.

[0297] The following are abbreviations of the compounds used in the synthesis examples and embodiments.

[0298] ODPA: 3,3',4,4'-Diphenyl ether tetracarboxylic acid dianhydride

[0299] 6FDA: 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride

[0300] BSAA: 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic acid) dianhydride

[0301] HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

[0302] PBOM: 1,1'-(4,4'-oxybenzoyl)diimidazole

[0303] DAE: 4,4'-Diaminodiphenyl ether

[0304] TFMB: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl

[0305] BAP: 2,2'-bis(3-amino-4-hydroxyphenyl)propane

[0306] Versamine 551: A dimeric diamine compound comprising the compound represented by formula (10) above (trade name, manufactured by BASF Corporation) (average amine value: 205)

[0307] Priamine 1075: A dimeric diamine compound containing the compound represented by formula (9) above (trade name, manufactured by Croda Japan Co., Ltd.) (average amine value: 205)

[0308] 6FAP: Bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0309] BIS-AT-AF: Bis(3-amino-4-methylphenyl)hexafluoropropane

[0310] DACH: Diaminocyclohexane

[0311] TAPOB-A: 1,3,5-Tris(4-aminophenoxy)benzene

[0312] MAP: m-Aminophenol

[0313] MeA: Methacrylic anhydride

[0314] GMA: Glycidyl methacrylate

[0315] Karenz MOI: 2-Methacryloxyethyl isocyanate (trade name, manufactured by Showa Denko Co., Ltd.)

[0316] NCI-831: Oxime ester-based photopolymerization initiator (trade name, manufactured by ADEKA Co., Ltd.)

[0317] IRGANOX3114: Hindered phenolic antioxidant (trade name, manufactured by BASF Corporation)

[0318] DCP-A: Dicyclopentadiene dimethacrylate (trade name, manufactured by Kyoei Chemical Co., Ltd.)

[0319] 4G: Tetraethylene glycol dimethacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0320] NIKALAC MW-100LM: A thermal crosslinking agent having an alkoxymethyl structure represented by the following chemical formula (trade name, manufactured by Sanwa Chemical Co., Ltd.)

[0321] [Chemical Formula 34]

[0322]

[0323] NMP: N-methyl-2-pyrrolidone

[0324] THF: Tetrahydrofuran

[0325] CP: Cyclopentanone

[0326] PGMEA: Propylene Glycol Methyl Ether Acetate

[0327] Polyflow 77: Acrylic surfactant (trade name, manufactured by Kyoei Chemical Co., Ltd.)

[0328] [Synthesis Example 1: Synthesis of Polyimide Resin (P-1)]

[0329] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 20 g of NMP was added along with 38.32 g (0.140 mol, based on amino group) of Versamine 551 and 9.16 g (0.025 mol) of 6FAP, and the reaction was carried out at 60 °C for 2 hours. The temperature was then raised to 200 °C, and the reaction was carried out for 3 hours. The solution was then cooled to 40 °C, and under a pressurized air atmosphere, 49.65 g of NMP was added along with 7.71 g (0.05 mol) of MeA, and the reaction was carried out at 40 °C for 2 hours. After the reaction was complete, the solution was cooled to room temperature, and 3 L of water was added to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polyimide resin (P-1) powder.

[0330] [Synthetic Example 2: Synthesis of Polyimide Precursor (P-2)]

[0331] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. Then, 5 g of NMP was added along with 1.09 g (0.010 mol) of MAP, and the mixture was reacted at 60 °C for 15 minutes. Next, 38.32 g (0.140 mol, based on amino groups) of Versamine 551, 9.16 g (0.025 mol) of 6FAP, and 20 g of NMP were added, and the mixture was reacted at 60 °C for 2 hours. Then, a solution prepared by diluting 21.45 g (0.180 mol) of N,N-dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd.) with 20 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 60 °C for 3 hours. Then, the mixture was cooled to 40°C, and under pressurized air, 29.65 g of NMP was added along with 7.71 g (0.05 mol) of MeA. The reaction was carried out at 40°C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solution was added to 3 L of water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for 3 days to obtain polyimide resin (P-2) powder.

[0332] [Synthetic Example 3: Synthesis of Polybenzoxazole Precursor (P-3)]

[0333] Under a dry nitrogen stream, 22.93 g (0.100 mol) of PBOM was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 85 °C for 15 minutes. Then, 20 g of NMP was added along with 38.32 g (0.140 mol, based on amino groups) of Versamine 551 and 9.16 g (0.025 mol) of 6FAP, and the reaction was carried out at 85 °C for 3 hours. The solution was then cooled to 40 °C, and under a pressurized air stream, 29.65 g of NMP was added along with 7.71 g (0.05 mol) of MeA, and the reaction was carried out at 40 °C for 2 hours. After the reaction was complete, the solution was cooled to room temperature, and 3 L of water was added to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried for three days in a ventilated dryer at 50°C to obtain a powder of polybenzoxazole precursor (P-3).

[0334] [Synthesis Example 4: Synthesis of Polybenzoxazole Resin (P-4)]

[0335] Under a dry nitrogen atmosphere, 22.93 g (0.100 mol) of PBOM was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 85 °C for 15 minutes. Then, 20 g of NMP was added along with 19.16 g (0.070 mol, based on amino group) of Versamine 551 and 21.98 g (0.060 mol) of 6FAP, and the reaction was carried out at 85 °C for 3 hours. The temperature was then raised to 200 °C, and the reaction was carried out for 3 hours. The solution was then cooled to 40 °C, and under a pressurized air atmosphere, 29.65 g of NMP was added along with 7.71 g (0.05 mol) of MeA, and the reaction was carried out at 40 °C for 2 hours. After the reaction was complete, the solution was cooled to room temperature, and 3 L of water was added to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polybenzoxazole resin (P-4) powder.

[0336] [Synthesis Example 5: Synthesis of Polyimide Resin (P-5)]

[0337] Except for replacing Versamine 551 with Priamine 1075 in Synthesis Example 1, the same procedure was followed as in Synthesis Example 1 to obtain polyimide resin (P-5).

[0338] [Synthesis Example 6: Synthesis of Polyimide Resin (P-6)]

[0339] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 37.38 g (0.140 mol, based on amino group) of Priamine 1075, 9.16 g (0.025 mol) of 6FAP, and 20 g of NMP were added, and the reaction was carried out at 60 °C for 2 hours. The temperature was then raised to 200 °C, and the reaction was carried out for 3 hours. The solution was then cooled to 40 °C, and under a pressurized air atmosphere, 49.65 g of NMP was added along with 7.11 g (0.05 mol) of GMA and 0.51 g (0.005 mol) of triethylamine, and the reaction was carried out at 90 °C for 4 hours. After the reaction was complete, the solution was cooled to room temperature, and 3 L of water was added to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polyimide resin (P-6) powder.

[0340] [Synthesis Example 7: Synthesis of Polyimide Resin (P-7)]

[0341] Except for changing MeA in Synthesis Example 1 to Karenz MOI, the same procedure was followed as in Synthesis Example 1 to obtain polyimide resin (P-7).

[0342] [Synthesis Example 8: Synthesis of the diamine compound TAPOB-A]

[0343] Under a dry nitrogen stream, 15.42 g (0.100 mol) of MeA and 221 g of THF were added to a 300 mL round-bottom flask and mixed. Then, 39.95 g (0.100 mol) of TAPOB dissolved in 20 g of NMP was added dropwise. After the addition, the mixture was stirred at 40 °C for 3 hours. After the reaction was complete, the reaction solution and 300 g of saturated sodium bicarbonate aqueous solution were added to a separatory funnel for two extraction operations. After extraction, the reaction solution was purified by alumina gel column chromatography, and then distilled under reduced pressure using a rotary evaporator to obtain 30.38 g of viscous liquid TAPOB-A (yield 65%).

[0344] [Chemical Formula 35]

[0345]

[0346] [Synthetic Example 9: Synthesis of Polyimide Precursor (P-8)]

[0347] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 20 g of NMP was added along with 38.32 g (0.140 mol, based on amino group) of Priamine 1075 and 11.69 g (0.025 mol) of TAPOB-A, and the reaction was carried out at 60 °C for 2 hours. Next, a solution prepared by diluting 21.45 g (0.180 mol) of N,N-dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd.) with 20 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 60 °C for 3 hours. After the reaction was complete, the solution was cooled to room temperature and added to 3 L of water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polyimide precursor (P-8) powder.

[0348] [Synthesis Example 10: Synthesis of Polyimide Resin (P-9)]

[0349] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 20 g of NMP was added along with 19.16 g (0.07 mol as amino), 7.01 g (0.035 mol) of DAE, and 9.16 g (0.025 mol) of 6FAP, and the reaction was carried out at 60 °C for 2 hours. The temperature was then raised to 200 °C, and the reaction was carried out for 3 hours. The solution was then cooled to 40 °C, and under pressurized air, 49.65 g of NMP was added along with 7.76 g (0.05 mol) of Karenz MOI, and the reaction was carried out at 40 °C for 2 hours. After the reaction was complete, the solution was cooled to room temperature, and 3 L of water was added to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polyimide resin (P-9) powder.

[0350] [Synthesis Examples 11-15: Synthesis of polyimide resins (P-10) to (P-14)]

[0351] Polyimide resins (P-10) to (P-14) were synthesized using the same molar ratios as in Synthesis Example 10, as shown in Table 2 below.

[0352] [Synthesis Example 16: Synthesis of Polyimide Resin (P-15)]

[0353] Except for changing 6FAP to BAP in Synthesis Example 13, the same procedure was followed as in Synthesis Example 13 to obtain polyimide resin (P-15).

[0354] [Synthesis Example 17: Synthesis of Polyimide Resin (P-16)]

[0355] Under a dry nitrogen atmosphere, 52.05 g (0.100 mol) of BSAA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 20 g of NMP was added along with 8.21 g (0.030 mol as amino), 11.01 g (0.055 mol) of DAE, and 9.16 g (0.025 mol) of 6FAP, and the reaction was carried out at 60 °C for 2 hours. The temperature was then increased to 200 °C, and the reaction was carried out for 3 hours. The mixture was then cooled to 40 °C, and under a pressurized air atmosphere, 49.65 g of NMP was added along with 7.76 g (0.05 mol) of Karenz MOI, and the reaction was carried out at 40 °C for 2 hours. After the reaction was completed, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polyimide resin (P-16) powder.

[0356] [Synthesis Example 18: Synthesis of Polyimide Resin (P-17)]

[0357] Except for changing BSAA to 6FDA in Synthesis Example 17, the same procedure as in Synthesis Example 16 was followed to obtain polyimide resin (P-17).

[0358] [Synthesis Example 19: Synthesis of Polyimide Resin (P-18)]

[0359] Except for replacing BSAA with HPMDA in Synthesis Example 17, the same procedure as in Synthesis Example 16 was followed to obtain polyimide resin (P-18).

[0360] [Synthesis Example 20: Synthesis of Polyimide Resin (P-19)]

[0361] Except for changing DAE to DACH in Synthesis Example 13, the same procedure was followed as in Synthesis Example 13 to obtain polyimide resin (P-19).

[0362] [Synthesis Example 21: Synthesis of Polyimide Resin (P-20)]

[0363] Except for changing DAE to TFMB in Synthesis Example 13, the same procedure was followed as in Synthesis Example 13 to obtain polyimide resin (P-20).

[0364] [Synthesis Example 22: Synthesis of Polyimide Resin (P-21)]

[0365] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 8.21 g (0.015 mol as amino) of Priamine 1075, 12.67 g (0.035 mol) of BIS-AT-AF, 16.48 g (0.045 mol) of 6FAP, and 20 g of NMP were added, and the reaction was carried out at 60 °C for 2 hours. The temperature was then raised to 200 °C, and the reaction was carried out for 3 hours. The mixture was then cooled to 40 °C, and under a pressurized air atmosphere, 49.65 g of NMP was added along with 15.52 g (0.010 mol) of Karenz MOI, and the reaction was carried out at 40 °C for 2 hours. After the reaction was completed, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain polyimide resin (P-21) powder.

[0366] [Synthesis Examples 23-27: Synthesis of polyimide resins (P-22) to (P-26)]

[0367] Polyimide resins (P-22) to (P-26) were synthesized using the same molar ratios as in Synthesis Example 22, as shown in Table 2 below.

[0368] [Synthesis Example 28: Synthesis of Polyimide Resin (P-27)]

[0369] Under a dry nitrogen atmosphere, 31.02 g (0.100 mol) of ODPA was dissolved in 234.67 g of NMP at 60 °C. 5 g of NMP was added to this solution along with 1.09 g (0.010 mol) of MAP, and the reaction was carried out at 60 °C for 15 minutes. Then, 20 g of NMP was added along with 38.32 g (0.140 mol, based on amino group) of Versamine 551 and 9.16 g (0.025 mol) of 6FAP, and the reaction was carried out at 60 °C for 2 hours. The temperature was then raised to 200 °C, and the reaction was carried out for 3 hours. After the reaction was complete, the solution was cooled to room temperature and added to 3 L of water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a ventilated dryer at 50 °C for 3 days to obtain polyimide resin (P-27) powder.

[0370] [Synthesis Example 29: Synthesis of Polyimide Resin (P-28)]

[0371] Except for replacing Priamine 1075 with DAE in Synthesis Example 21, the same procedure was followed as in Synthesis Example 21 to obtain polyimide resin (P-28).

[0372] [Example 1]

[0373] Under yellow light, 10.00 g of polyimide resin (P-1), 0.5 g of NCI-831, 0.10 g of IRGANOX 3114, and 0.30 g of 3-trimethoxysilyl phthalic acid were dissolved in 18.96 g of NMP. 0.10 g of a 1% EL solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The properties of the obtained varnish were determined using the above evaluation methods, including pattern processability, dielectric constant, dielectric loss tangent, and elongation at break.

[0374] [Example 2]

[0375] The procedure is the same as in Example 1, except that P-1 is replaced with P-2.

[0376] [Example 3]

[0377] The procedure is the same as in Example 1, except that P-1 is replaced with P-3.

[0378] [Example 4]

[0379] The procedure is the same as in Example 1, except that P-1 is replaced with P-4.

[0380] [Example 5]

[0381] The procedure is the same as in Example 1, except that P-1 is replaced with P-5.

[0382] [Example 6]

[0383] The procedure is the same as in Example 1, except that P-1 is replaced with P-6.

[0384] [Example 7]

[0385] The procedure is the same as in Example 1, except that P-1 is replaced with P-7.

[0386] [Example 8]

[0387] The procedure is the same as in Example 1, except that P-1 is replaced with P-8.

[0388] [Example 9]

[0389] The procedure is the same as in Example 1, except that P-1 is replaced with P-9.

[0390] [Example 10]

[0391] The procedure is the same as in Example 1, except that P-1 is replaced with P-10.

[0392] [Example 11]

[0393] The procedure is the same as in Example 1, except that P-1 is replaced with P-11.

[0394] [Example 12]

[0395] The procedure is the same as in Example 1, except that P-1 is replaced with P-12.

[0396] [Example 13]

[0397] The procedure is the same as in Example 1, except that P-1 is replaced with P-13.

[0398] [Example 14]

[0399] The procedure is the same as in Example 1, except that P-1 is replaced with P-14.

[0400] [Example 15]

[0401] The procedure is the same as in Example 1, except that P-1 is replaced with P-15.

[0402] [Example 16]

[0403] The procedure is the same as in Example 1, except that P-1 is replaced with P-16.

[0404] [Example 17]

[0405] The procedure is the same as in Example 1, except that P-1 is replaced with P-17.

[0406] [Example 18]

[0407] The procedure is the same as in Example 1, except that P-1 is replaced with P-18.

[0408] [Example 19]

[0409] The procedure is the same as in Example 1, except that P-1 is replaced with P-19.

[0410] [Example 20]

[0411] The procedure is the same as in Example 1, except that P-1 is replaced with P-20.

[0412] [Example 21]

[0413] The procedure is the same as in Example 1, except that P-1 is replaced with P-21.

[0414] [Example 22]

[0415] The procedure is the same as in Example 1, except that P-1 is replaced with P-22.

[0416] [Example 23]

[0417] The procedure is the same as in Example 1, except that P-1 is replaced with P-23.

[0418] [Example 24]

[0419] The procedure is the same as in Example 1, except that P-1 is replaced with P-24.

[0420] [Example 25]

[0421] The procedure is the same as in Example 1, except that P-1 is replaced with P-25.

[0422] [Example 26]

[0423] The procedure is the same as in Example 1, except that P-1 is replaced with P-26.

[0424] [Example 27]

[0425] Under yellow light, 10.00 g of polyimide resin (P-21), 0.5 g of NCI-831, 0.10 g of IRGANOX 3114, 0.30 g of 3-trimethoxysilyl phthalic acid, and 0.5 g of MW-100LM were dissolved in 18.96 g of NMP. 0.10 g of a 1% EL solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The properties of the obtained varnish were determined using the above evaluation methods, including pattern processability, dielectric constant, dielectric loss tangent, and elongation at break.

[0426] [Example 28]

[0427] The same procedure as in Example 27 is followed, except that P-21 is replaced with P-23.

[0428] [Example 29]

[0429] The same procedure as in Example 27 is followed, except that P-21 is replaced with P-25.

[0430] [Example 30]

[0431] Under yellow light, 8.00 g of polyimide resin (P-16), 2.00 g of 4G, 0.5 g of NCI-831, 0.10 g of IRGANOX 3114, and 0.30 g of 3-trimethoxysilyl phthalic acid were dissolved in 18.96 g of NMP. 0.10 g of a 1% EL solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The properties of the obtained varnish were determined using the above evaluation methods, including pattern processability, dielectric constant, dielectric loss tangent, and elongation at break.

[0432] [Example 31]

[0433] Except for replacing 4G with DCP-A, it is implemented in the same way as in Example 30.

[0434] [Comparative Example 1]

[0435] The procedure is the same as in Example 1, except that P-1 is replaced with P-28.

[0436] [Comparative Example 2]

[0437] The procedure is the same as in Example 1, except that P-1 is replaced with P-29.

[0438] The composition and evaluation results of Example 1 and the comparative examples are shown in Tables 2 to 4 below.

[0439] [Table 2]

[0440]

[0441] [Table 3-1]

[0442] Table 3-1

[0443]

[0444] [Table 3-2]

[0445] Table 3-2

[0446] [Table 4-1]

[0447] Table 4-1

[0448] [Table 4-2]

[0449] Explanation of reference numerals in the attached figures

[0450] 1. Silicon wafer

[0451] 2 Al pads

[0452] 3. Passivation film

[0453] 4. Insulating film

[0454] 5. Metal (Cr, Ti, etc.) films

[0455] 6. Metallic wiring (Al, Cu, etc.)

[0456] 7. Insulating film

[0457] 8. Blocking metal

[0458] 9 lines

[0459] 10 Solder bumps

[0460] 11 Antenna Section

[0461] 12 Matching Circuit

[0462] 13 MSL power supply lines

[0463] 14 Power Supply Points

[0464] 15 Ground wire

[0465] 16 Insulating film

[0466] J Ground wire wiring thickness

[0467] K antenna wiring thickness

[0468] M Matching circuit length

[0469] L Antenna length

[0470] W antenna width

[0471] 201 IC Chip

[0472] 202 Electrode Pad

[0473] 203 Wiring in the second through hole

[0474] 204 Planar Antenna Wiring

[0475] 205 Second Sealing Resin

[0476] 206 ground wire

[0477] 207 Through-hole wiring

[0478] 208 First Sealing Resin

[0479] 209 Copper Wiring

[0480] 210 Insulating film

[0481] 211 Blocking Metal

[0482] 212 Solder bump.

Claims

1. A photosensitive resin composition comprising a resin (A3) and a photopolymerization initiator (B), wherein the resin (A3) comprises one or more structural units selected from the group consisting of structural units represented by formulas (1) and (3), and further comprises one or more structural units selected from the group consisting of structural units represented by formulas (2) and (4). In equation (1), X 1 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 1 X represents a divalent organic group with 2 to 70 carbon atoms. 1 and Y 1 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are replaced by hydrocarbon groups with 4 to 12 carbon atoms that may have unsaturated bonds. Indicates the bond point; In equation (2), X 2 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 2 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 1 and R 2 Each of the following groups independently represents a carboxyl group, a hydroxyl group, or an organic group with 3 to 30 monovalent carbon atoms having an alkene-type unsaturated bond; R 1 and R 2 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, where p represents an integer from 0 to 2, q represents an integer from 0 to 4, and 1 ≤ p + q ≤ 6. Indicates the bond point; In equation (3), X 3 Y represents a tetravalent organic group with 2 to 60 carbon atoms. 3 X represents a divalent organic group with 2 to 70 carbon atoms. 3 and Y 3 At least one of them represents a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon with 4 to 8 carbon atoms that may have unsaturated bonds, wherein at least 4 hydrogen atoms are replaced by hydrocarbon groups with 4 to 12 carbon atoms that may have unsaturated bonds. Indicates the bond point; In equation (4), X 4 Y represents an organic group with 2 to 60 carbon atoms and a valence of 4 to 6. 4 Represents organic groups with 2 to 70 carbon atoms and valences of 2 to 6, multiple R 3 and R 4 They can be the same or different, representing a carboxyl group, hydroxyl group, or an organic group with 3 to 30 carbon atoms in a monovalent state and an alkene-type unsaturated bond, R. 3 and R 4 At least one of them represents a monovalent organic group with 3 to 30 carbon atoms having an alkene-type unsaturated bond, where r represents an integer from 0 to 2, s represents an integer from 0 to 4, and 1 ≤ r + s ≤ 6. Indicates the bond point. in, Y in equation (1) 1 and Y in equation (3) 3 For the residues of the diamine represented by formula (8) that do not contain double bonds, In equation (8), e', f', g', and h' are natural numbers, e'+f' = 6 to 17, and g'+h' = 8 to 19; the dashed part refers to carbon-carbon single bonds.

2. The photosensitive resin composition according to claim 1, wherein, The total structural units of resin (A3) are 1 to 15 mol% of one or more structural units selected from the group consisting of structural units represented by formulas (1) and (3), relative to 100 mol% of all structural units.

3. The photosensitive resin composition according to claim 1 or 2, wherein, Y in equation (1) 1 and Y in equation (3) 3 For the residues of the diamine represented by formula (9), 。 4. The photosensitive resin composition according to claim 1 or 2, wherein, When the resin (A3) contains the structural unit represented by formula (2), there are multiple R... 1 and R 2 At least one of them is a group represented by formula (12) or formula (13), When the resin (A3) contains the structural unit represented by formula (4), there are multiple R... 3 and R 4 At least one of them is a group represented by formula (12) or formula (13), In equation (12), R 9 R represents the bonding group represented by -OCH2CH(OH)-, -OCONH-, -NHCH2CH(OH)-, or -NHCONH-. 10 R 11 and R 12 Each represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and 'a' represents an integer from 1 to 10. Indicates the bond point; In equation (13), R 13 R represents the bonding group represented by -OCO- or -NHCO-. 14 R 15 and R 16 Each represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and b represents an integer from 0 to 10. Indicates the bond point.

5. The photosensitive resin composition according to claim 1 or 2, wherein, In equations (1) to (4), X 1 ~X 4 Comprising residues selected from the group consisting of residues chosen from the bisphenol A backbone, biphenyl backbone, hexafluoroisopropylidene backbone, and anhydride represented by formula (14), or Y 1 ~Y 4 It comprises residues selected from the group consisting of residues of bisphenol A backbone, biphenyl backbone, hexafluoroisopropylidene backbone and diamine represented by formula (15). In equation (14), z represents an integer from 6 to 20. Indicates the bond point. In equation (15), Indicates the bond point.

6. The photosensitive resin composition according to claim 1 or 2, wherein, In equations (1) to (4), Y 1 ~Y 4 Either of them contains residues of the diamine represented by formula (16), In equation (16), R 17 and R 18 Each group independently represents a group selected from methyl, trifluoromethyl, or hydroxyl, and v and w represent integers from 0 to 4.

7. The photosensitive resin composition according to claim 1 or 2, wherein, The resin (A3) contains fluorine components in its structure.

8. The photosensitive resin composition according to claim 1 or 2, wherein, The resin (A3) has 1 to 25 mol% phenolic hydroxyl groups relative to 100 mol% of all structural units.

9. The photosensitive resin composition according to claim 1 or 2, further comprising a compound (C) having two or more olefinic unsaturated bonds and an alicyclic structure.

10. The photosensitive resin composition according to claim 1 or 2, further comprising a thermal crosslinking agent (D).

11. A photosensitive sheet formed on a substrate by forming the photosensitive resin composition of any one of claims 1 to 10.

12. A cured film, which is formed by curing the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive sheet according to claim 11.

13. A method for manufacturing a cured film, comprising using the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive sheet according to claim 11 to manufacture the cured film, the method comprising: The process of coating the photosensitive resin composition onto a substrate or laminating the photosensitive sheet onto a substrate and drying it to form a photosensitive resin film. The process includes: exposing the photosensitive resin film; developing the exposed photosensitive resin film; and heat-treating the developed photosensitive resin film.

14. An electronic component having the cured film as claimed in claim 12.

15. An antenna element comprising at least one antenna wiring and the cured film of claim 12, wherein the antenna wiring comprises at least one selected from the group consisting of a zigzag loop antenna, a coil loop antenna, a zigzag monopole antenna, a zigzag dipole antenna, and a microstrip antenna, and each antenna portion of the antenna wiring has a proprietary area of ​​1000 mm². 2 The cured film is described below as an insulating film that insulates the ground wire from the antenna wiring.

16. A semiconductor package, comprising at least a semiconductor element, a redistribution layer, a sealing resin, and antenna wiring. The antenna wiring includes at least one selected from the group consisting of a zigzag loop antenna, a coil loop antenna, a zigzag monopole antenna, a zigzag dipole antenna, and a microstrip antenna. The dedicated area for each antenna section in this antenna wiring is 1000 mm². 2 Hereinafter, the insulating layer of the redistribution layer and / or the sealing resin comprises the cured film of claim 12, the sealing resin being located between the ground wire and the antenna wiring.

17. An antenna element, wherein an antenna element is obtained by laminating antenna wiring with the cured film of claim 12, wherein, The antenna wiring height is 50–200 μm, and the thickness of the cured film is 80–300 μm.

18. A display device comprising the cured film of claim 12.

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