Photosensitive resin composition, photosensitive sheet, cured film, method for manufacturing a cured film, electronic component, antenna element, semiconductor package, and display device.

Abstract

The purpose of the present invention is to provide a photosensitive resin composition that yields a cured film having exceptional heat resistance, elongation, chemical resistance, permittivity, and dielectric tangent while being curable under low-temperature heat treatments, the percentage of film remaining after development being exceptional. To solve the above problem, the photosensitive resin composition of the present invention has the following configuration. Specifically, a photosensitive resin composition that contains a resin (A) and a photopolymerization initiator (B), said resin (A): containing one or more structural units selected from the group consisting of specific structural units represented by formula (1), formula (3), and formula (5); and also containing one or more structural units selected from the group consisting of structural units represented by formula (2), formula (4), and formula (6).

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive sheet, a cured film, a method for manufacturing a cured film, an antenna element, a semiconductor package, an electronic component, and a display device. More specifically, the present invention relates to a photosensitive resin composition suitably used as a surface protective film or interlayer insulating film for electronic components such as semiconductor elements, and as an insulating layer for organic EL elements. [Background technology]

[0002] Polyimide resins, which have excellent heat resistance and electrical insulation properties, are typical materials for surface protective films and interlayer insulating films of semiconductor devices, insulating layers of organic electrolytic devices, and planarization films of TFT substrates. Furthermore, to improve productivity, research is being conducted on photosensitive polyimides and their precursors that impart negative photosensitivity.

[0003] In recent years, with the expansion of semiconductor applications and improvements in performance, efforts have been made to reduce costs and increase integration through the efficiency of manufacturing processes. As a result, semiconductor devices that form multilayer metal redistributions are attracting attention. The insulating films of such multilayer metal redistributions require low dielectric constants to accommodate high integration. Furthermore, in high-frequency communication devices for high-speed wireless communication, low dielectric loss tangents of the insulating films are required to reduce transmission loss. In addition, given that mold resins used in memory devices and semiconductor package manufacturing are susceptible to high-temperature processes, there is a demand for polyimide resins and polybenzoxazole resins that can be cured by firing at low temperatures of 250°C or less, and more preferably 220°C or less, and that possess high mechanical properties, thermal properties, and chemical resistance for surface protective films and interlayer insulating films.

[0004] Means for lowering dielectric constant and dielectric loss tangent include photosensitive resin compositions in which a specific chemical structure is introduced into a part of the side chain of the polyimide precursor (Patent Document 1) and soluble polyimides using dimer amine (Patent Document 2). Examples of resin compositions that can be cured at low temperatures include resin compositions containing polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, and a thermal crosslinking agent (Patent Document 3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2019 / 044874 [Patent Document 2] Japanese Patent Publication No. 2018-203959 [Patent Document 3] Japanese Patent Publication No. 2007-16214 [Overview of the project] [Problems that the invention aims to solve]

[0006] When conventional technologies are applied as multilayer wiring insulating films for high-frequency communication devices for high-speed wireless communication, for example, Patent Document 1 suffers from insufficient chemical resistance and mechanical properties due to insufficient imide ring closure during low-temperature curing; Patent Document 2 fails to achieve sufficient heat resistance and residual film rate after development due to the flexible skeleton derived from dimeramine; and Patent Document 3 has the problem of high dielectric constant and dielectric loss tangent. [Means for solving the problem]

[0007] To solve the aforementioned problems, the present invention is as follows. (1) A photosensitive resin composition comprising a resin (A1) and a photopolymerization initiator (B), wherein the resin has a structural unit represented by general formula (17) and has an ethylenically unsaturated bond, and the precursor has a bond derived from an ethylenically unsaturated bond even after imidization or oxazoleization.

[0008] [ka]

[0009] In equation (17), c, d, e, and f are integers greater than or equal to 1 such that c+d=6 to 17 and e+f=8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. (2) A photosensitive resin composition containing a resin (A2) having at least one of the structural units represented by formulas (18), (19), and (20), and having a structural unit represented by formula (17), and a photopolymerization initiator (B).

[0010] [ka]

[0011] In equation (17), c, d, e, and f are integers greater than or equal to 1 such that c+d=6 to 17 and e+f=8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0012] [ka]

[0013] In formula (18), X 8 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 8 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, and multiple R 19 and R 20Each independently represents a monovalent organic group having 3 to 30 carbon atoms with a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond, R 19 and R 20 at least one of which represents a monovalent organic group having 3 to 30 carbon atoms with an ethylenically unsaturated bond, g represents an integer of 0 to 2, h represents an integer of 0 to 4, 1 ≦ g + h ≦ 6, and * represents a bonding point.

[0014]

Chemical formula

[0015] In formula (19), X 9 represents a tetravalent to hexavalent organic group having 2 to 60 carbon atoms, Y 9 represents a divalent to hexavalent organic group having 2 to 70 carbon atoms, and a plurality of R 21 and R 22 may be the same or different from each other, and each represents a monovalent organic group having 3 to 30 carbon atoms with a carboxyl group, a hydroxyl group or an ethylenically unsaturated bond, R 21 and R 22 at least one of which represents a monovalent organic group having 3 to 30 carbon atoms with an ethylenically unsaturated bond, i represents an integer of 0 to 2, j represents an integer of 0 to 4, 1 ≦ i + j ≦ 6, and * represents a bonding point.

[0016]

Chemical formula

[0017] In formula (20), X 10 represents a tetravalent to hexavalent organic group having 2 to 60 carbon atoms, Y 10 represents a divalent to hexavalent organic group having 2 to 70 carbon atoms, (COOR 23 ) is a substituent at a position capable of forming an amide group and an imide ring that binds to X 10 , R 23 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms, R 24 represents a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms, R 25R represents a carboxyl group, a hydroxyl group, or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms. 24 and R 25 At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically unsaturated bond, k is an integer from 0 to 2, x is an integer from 0 to 2, y is an integer from 0 to 4, 1 ≤ x + y ≤ 6, and * represents a bond point. (3) A photosensitive resin composition comprising a resin (A3) containing one or more structural units selected from the group consisting of structural units represented by formulas (1), (3), and (5), and further comprising one or more structural units selected from the group consisting of structural units represented by formulas (2), (4), and (6), and a photopolymerization initiator (B).

[0018] [ka]

[0019] In formula (1), X 1 This represents a tetravalent organic group with 2 to 60 carbon atoms, Y 1 This represents a divalent organic group with 2 to 70 carbon atoms, X 1 and Y 1 At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bond site.

[0020] [ka]

[0021] In formula (2), X 2 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 2 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, and multiple R 1 and R 2Each of these independently represents a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond, R 1 and R 2 At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically unsaturated bond, p is an integer from 0 to 2, q is an integer from 0 to 4, 1 ≤ p + q ≤ 6, and * represents a bond point.

[0022] [ka]

[0023] In formula (3), X 3 This represents a tetravalent organic group with 2 to 60 carbon atoms, Y 3 This represents a divalent organic group with 2 to 70 carbon atoms, X 3 and Y 3 At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bond site.

[0024] [ka]

[0025] In formula (4), X 4 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 4 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, and multiple R 3 and R 4 These may be the same or different, and represent a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond, R 3 and R 4 At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically unsaturated bond, r is an integer from 0 to 2, s is an integer from 0 to 4, 1 ≤ r + s ≤ 6, and * represents a bond point.

[0026] [ka]

[0027] In formula (5), X 5 This represents a tetravalent organic group with 2 to 60 carbon atoms, Y 5 This represents a divalent organic group with 2 to 70 carbon atoms, X 5 and Y 5 At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, and in the structure of the cycloaliphatic hydrocarbon, at least four or more hydrogen atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, (COOR 5 ) is X 5 A substituent located in a position where it can form an imide ring with an amide group that bonds to it, R 5 * indicates a hydrogen atom or an organic group with 1 to 5 carbon atoms, and * indicates a bonding point.

[0028] [ka]

[0029] In formula (6), X 6 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 6 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, (COOR 6 ) is X 6 A substituent located in a position where it can form an imide ring with an amide group that bonds to it, R 6 R represents a hydrogen atom or an organic group with 1 to 5 carbon atoms. 7 R represents a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms, 8 R represents a carboxyl group, a hydroxyl group, or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms. 7 and R 8 At least one of the atoms has an ethylenically unsaturated bond with 3 to 30 carbon atoms, t is an integer from 0 to 2, u is an integer from 0 to 4, 1 ≤ t + u ≤ 6, and * indicates a bond point. [Effects of the Invention]

[0030] The photosensitive resin composition of the present invention has a high residual film rate after development. Furthermore, its cured film exhibits excellent heat resistance, chemical resistance, dielectric constant, and dielectric loss tangent. [Brief explanation of the drawing]

[0031] [Figure 1] This is a diagram showing an enlarged cross-section of the pad portion of a semiconductor device having bumps. [Figure 2] This figure shows a detailed method for fabricating a semiconductor device having bumps. [Figure 3] Figure 3 is a schematic diagram of a coplanar-fed microstrip antenna, which is a type of planar antenna. [Figure 4] Figure 4 is a schematic diagram of a cross-section of a semiconductor package comprising an IC chip (semiconductor element), rewiring, sealing resin, and an antenna element. [Modes for carrying out the invention]

[0032] The photosensitive resin composition of the present invention is a resin comprising at least one selected from polyimides, polybenzoxazoles, their precursors, and copolymers thereof, having a structural unit represented by general formula (17) and having an ethylenically unsaturated bond, wherein the precursor retains a bond derived from an ethylenically unsaturated bond even after imidization or oxazoleization, and contains a resin (A1) (hereinafter sometimes abbreviated as "component (A1)") and a photopolymerization initiator (B) (hereinafter sometimes abbreviated as "component (B)").

[0033] [ka]

[0034] In equation (17), c, d, e, and f are integers greater than or equal to 1 satisfying c+d=6 to 17 and e+f=8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. In this specification, the notation "~" means that the upper and lower limits are included unless otherwise specified.

[0035] Polyimides and polybenzoxazoles are resins that have a cyclic structure of either an imide ring or an oxazole ring in their main chain structure. Their precursors, polyimide precursors and polybenzoxazole precursors, are resins that form imide and benzoxazole ring structures, respectively, through dehydration and cyclization.

[0036] Polyimides can be obtained by reacting tetracarboxylic acids, tetracarboxylic dianhydrides, tetracarboxylic diester dichlorides, etc., with diamines, diisocyanate compounds, trimethylsilylated diamines, etc., and have tetracarboxylic acid residues and diamine residues. For example, polyimides can be obtained by dehydrating and cyclizing polyamic acid, one of the polyimide precursors obtained by reacting tetracarboxylic dianhydrides with diamines, through heat treatment. During this heat treatment, a solvent that forms an azeotrope with water, such as m-xylene, can also be added. Alternatively, dehydration and cyclization can be performed by chemical heat treatment with the addition of a dehydration condensing agent such as a carboxylic acid anhydride or dicyclohexylcarbodiimide, or a cyclization catalyst such as a base such as triethylamine. Or, dehydration and cyclization can be performed by adding a weakly acidic carboxylic acid compound and heat treatment at a low temperature of 100°C or lower.

[0037] Furthermore, copolymers can be formed by adjusting the reaction time during the dehydration and ring-closing process described above, or by polymerizing polyimide followed by the polymerization of polyamic acid.

[0038] Known tetracarboxylic dianhydrides can be used. For example, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic acid dianhydride, bicyclohexanetetracarboxylic 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'-oxydiphthalic anhydride, p-phenylenebis(trimellitate anhydride), ethylene glycol bis-anhydrotrimellitate, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride are examples. These compounds may be used individually or in combination of two or more.

[0039] As the diamine, any known type can be used. Examples include, but are not limited to, 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-tolidine, 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-methanoindanidinemethylenediamine. These compounds may be used individually or in combination of two or more.

[0040] Polybenzoxazoles can be obtained by reacting bisaminophenol compounds with dicarboxylic acids, dicarboxylic acid chlorides, or dicarboxylic acid active esters, and they contain dicarboxylic acid residues and bisaminophenol residues. For example, polybenzoxazole can be obtained by dehydrating and cyclizing polyhydroxyamide, one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, through heat treatment. Alternatively, dehydration and cyclization can be achieved by chemical treatment with the addition of phosphoric anhydride, a base, or a carbodiimide compound.

[0041] Furthermore, copolymers can be obtained by adjusting the reaction time during the dehydration and ring-closing process described above, or by polymerizing polybenzoxazole followed by the polymerization of polyhydroxyamide.

[0042] Known dicarboxylic acids can be used. For example, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc. These compounds may be used individually or in combination of two or more.

[0043] Known bisaminophenol compounds can be used. For example, 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., are examples but are not limited to these. These compounds may be used individually or in combination of two or more.

[0044] Furthermore, by combining tetracarboxylic dianhydride, dicarboxylic acid, and diamine, copolymers consisting of two or more of the following can be obtained: polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

[0045] The precursor retains bonds derived from ethylenically unsaturated bonds even after imidation or oxazole. The presence of ethylenically unsaturated bonds after imidation or oxazole allows for improved heat resistance during curing through crosslinking between resins.

[0046] Known methods for introducing ethylenically unsaturated bonds into a resin include reacting hydroxyl groups and / or carboxyl groups in the resin with a compound having an ethylenically unsaturated double bond group, and polymerizing a resin using a monomer having an ethylenically unsaturated bond. From the viewpoint of reactivity, electrophilic compounds having an ethylenically unsaturated double bond group are preferred as the compound having the ethylenically unsaturated double bond group.

[0047] Examples of electrophilic compounds include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thioketone compounds, acetate compounds, carboxylic acid chlorides, carboxylic acid anhydrides, carboxylic acid active ester compounds, carboxylic acid compounds, alkyl halogenated compounds, alkyl azide compounds, triflate alkyl compounds, mesylate alkyl compounds, tosylate alkyl compounds, or alkyl cyanide compounds. However, from the viewpoint of reactivity and the usability of the compounds, isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds, or carboxylic acid anhydrides are preferred, and isocyanate compounds, epoxy compounds, and carboxylic acid anhydrides are more preferred.

[0048] A small amount of polymerization inhibitor may be used to prevent crosslinking of ethylenically unsaturated bond sites during the reaction. Examples of polymerization inhibitors include phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. The amount of polymerization inhibitor added is preferably such that the phenolic hydroxyl groups of the polymerization inhibitor are between 0.1 mol% and 5 mol% relative to the ethylenically unsaturated bonds of the alcohols.

[0049] Formula (17) is a structure having a dimer acid skeleton, which is a dimer of an unsaturated fatty acid such as linoleic acid or oleic acid. From the viewpoint of the reliability of the resulting cured film, a structure that does not contain a double bond is preferred.

[0050] Specific examples of diamines having the structure shown in formula (17) include commercially available dimer amines such as "Versamin® 551" and "Versamin® 552" manufactured by BASF Ltd., and "Priamine® 1073," "Priamine® 1074," and "Priamine® 1075" manufactured by Croda Japan Ltd. Here, "Versamin® 551" and "Priamine® 1074" are both dimer amine compounds containing the compound represented by formula (10), and "Versamin® 552," "Priamine® 1073," and "Priamine® 1075" are all dimer amine compounds containing the compound represented by formula (9).

[0051] [ka]

[0052] [ka]

[0053] Alternatively, a mixture of trimertriamine and dimeramine may be used. A commercially available product containing trimertriamine and dimeramine is "Priamine® 1071" manufactured by Croda Japan Co., Ltd.

[0054] Specific examples of polycarboxylic acids having the structure shown in formula (17) include “Pripol®” 1009, “Pripol®” 1006, “Pripol®” 1010, “Pripol®” 1013, “Pripol®” 1025, “Pripol®” 1017, “Pripol®” 1040, and “Pripol®” 1004, all manufactured by Croda Japan Co., Ltd.

[0055] Examples of polycarboxylic acid derivatives having the structure shown in formula (17) include the reaction products of the dimer amines and trimellitic anhydride chloride exemplified above. More specifically, they are shown in formula (11).

[0056] [ka]

[0057] In equation (11), i', j', k', and l' are natural numbers, where i'+j'=6 to 17 and k'+l'=8 to 19. The wavy lines indicate carbon-carbon single bonds or carbon-carbon double bonds.

[0058] In resin (A1), the content of the structural unit represented by formula (17) is preferably 1 mol% or more and 30 mol% or less, and more preferably 1 mol% or more and 15 mol% or less. By increasing the content to 1 mol% or more, the relative permittivity and dielectric loss tangent can be lowered. Furthermore, by reducing the content to 30 mol% or less, the heat resistance can be increased.

[0059] The photosensitive resin composition of the present invention contains a resin (A2) having at least one of the structural units represented by formulas (18), (19), and (20), and having a structural unit represented by formula (17) (hereinafter sometimes abbreviated as "component (A2)"), and a photopolymerization initiator (B).

[0060] [ka]

[0061] In formula (18), X 8 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 8 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, and multiple R 19 and R 20 Each of these independently represents a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond, R 19 and R 20At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically 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 bond point.

[0062] [ka]

[0063] In formula (19), X 9 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 9 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, and multiple R 21 and R 22 These may be the same or different, and represent a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond, R 21 and R 22 At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically unsaturated bond, i is an integer from 0 to 2, j is an integer from 0 to 4, 1 ≤ i + j ≤ 6, and * represents a bond point.

[0064] [ka]

[0065] In formula (20), X 10 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 10 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, (COOR 23 ) is X 10 A substituent located in a position where it can form an imide ring with an amide group that bonds to it, R 23 R represents a hydrogen atom or an organic group with 1 to 5 carbon atoms. 24 R represents a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms, 25 R represents a carboxyl group, a hydroxyl group, or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms. 24 and R 25At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically unsaturated bond, k is an integer from 0 to 2, x is an integer from 0 to 2, y is an integer from 0 to 4, 1 ≤ x + y ≤ 6, and * represents a bond point.

[0066] An organic group is a group containing at least carbon atoms, and may further contain oxygen atoms, hydrogen atoms, fluorine atoms, and other atoms as needed. Furthermore, an X-valent organic group is a group whose chemical structure is formed when an organic compound takes the form of an X-valent group, and refers to an atomic group obtained by removing X hydrogen atoms from an organic compound.

[0067] The photosensitive resin composition of the present invention, by containing component (A2), results in a cured film of the present invention having a low dielectric constant and low dielectric loss tangent.

[0068] In equations (18), (19), and (20), X 8 , X 9 and X 10 This represents a tetravalent organic group with 2 to 60 carbon atoms, and indicates an acidic component residue. Examples of acidic components include tetracarboxylic acids, tetracarboxylic dianhydrides, or tetracarboxylic diester dichlorides.

[0069] Y 8 , Y 9 and Y 10 This represents a divalent organic group with 2 to 70 carbon atoms, and indicates an amine residue.

[0070] In resin (A2), the content of the structural unit represented by formula (17) is preferably 1 mol% or more and 30 mol% or less, and more preferably 1 mol% or more and 15 mol% or less. By increasing the content to 1 mol% or more, the relative permittivity and dielectric loss tangent can be lowered. Furthermore, by decreasing the content to 30 mol% or less, the heat resistance can be increased. In the aforementioned equation (18), R 19 and R 20 Alternatively, in equation (19), R 21 and R 22 Alternatively, in equation (20), R 24and R 25 By having an ethylenically unsaturated bond at any position of 25 , heat resistance can be improved by crosslinking of resins during curing.

[0071] As a method for introducing an ethylenically unsaturated bond into the resin, known methods such as reacting a hydroxyl group and / or a carboxyl group in the resin with a compound having an ethylenically unsaturated double bond group, or polymerizing using a monomer having an ethylenically unsaturated bond to obtain a resin can be mentioned. As the compound having an ethylenically unsaturated double bond group, from the viewpoint of reactivity, an electrophilic compound having an ethylenically unsaturated double bond group is preferable.

[0072] Examples of the electrophilic compound include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thioketone compounds, acetate compounds, carboxylic acid chlorides, carboxylic acid anhydrides, carboxylic acid active ester compounds, carboxylic acid compounds, alkyl halide compounds, alkyl azide compounds, alkyl triflate compounds, alkyl mesylate compounds, alkyl tosylate compounds or alkyl cyanide compounds. From the viewpoints of reactivity and availability of the compound, isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds or carboxylic acid anhydrides are preferable, and isocyanate compounds, epoxy compounds, carboxylic acid anhydrides are more preferable.

[0073] For the purpose of preventing crosslinking of the ethylenically unsaturated bond site during the reaction, a small amount of a polymerization inhibitor may be used. Examples of the polymerization inhibitor include phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. As the addition amount of the polymerization inhibitor, it is preferable that the phenolic hydroxyl group of the polymerization inhibitor is 0.1 mol% or more and 5 mol% or less with respect to the ethylenically unsaturated bond of the alcohols.

[0074] The photosensitive resin composition of the present invention contains one or more structural units selected from the group consisting of structural units represented by formula (1), formula (3), and formula (5), and further contains a resin (A3) (hereinafter, may be abbreviated as "(A3) component") containing one or more structural units selected from the group consisting of structural units represented by formula (2), formula (4), and formula (6), and a photopolymerization initiator (B).

[0075]

Chemical formula

[0076] In formula (1), X 1 represents a tetravalent organic group having 2 to 60 carbon atoms, Y 1 represents a divalent organic group having 2 to 70 carbon atoms, and at least one of X 1 and Y 1 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have an unsaturated bond. In the structure of the alicyclic hydrocarbon, at least 4 or more hydrogen atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have an unsaturated bond, and * represents a bonding point.

[0077] <s

Chemical formula

[0078] In formula (2), X 2 represents a tetravalent to hexavalent organic group having 2 to 60 carbon atoms, Y 2 represents a divalent to hexavalent organic group having 2 to 70 carbon atoms, a plurality of R 1 and R 2 each independently represent a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms having an ethylenic unsaturated bond, and at least one of R 1 and R 2 represents a monovalent organic group having 3 to 30 carbon atoms having an ethylenic unsaturated bond, p represents an integer of 0 to 2, q represents an integer of 0 to 4, 1 ≤ p + q ≤ 6, and * represents a bonding point.

[0079] [ka]

[0080] In formula (3), X 3 This represents a tetravalent organic group with 2 to 60 carbon atoms, Y 3 This represents a divalent organic group with 2 to 70 carbon atoms, X 3 and Y 3 At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bond site.

[0081] [ka]

[0082] In formula (4), X 4 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 4 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, and multiple R 3 and R 4 These may be the same or different, and represent a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond, R 3 and R 4 At least one of the elements represents a monovalent organic group with 3 to 30 carbon atoms having an ethylenically unsaturated bond, r is an integer from 0 to 2, s is an integer from 0 to 4, 1 ≤ r + s ≤ 6, and * represents a bond point.

[0083] The presence of ethylenically unsaturated bonds improves the residual film rate after development and enhances heat resistance through crosslinking of resins during curing.

[0084] [ka]

[0085] In formula (5), X5 This represents a tetravalent organic group with 2 to 60 carbon atoms, Y 5 This represents a divalent organic group with 2 to 70 carbon atoms, X 5 and Y 5 At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, and in the structure of the cycloaliphatic hydrocarbon, at least four or more hydrogen atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, (COOR 5 ) is X 5 A substituent located in a position where it can form an imide ring with an amide group that bonds to it, R 5 * indicates a hydrogen atom or an organic group with 1 to 5 carbon atoms, and * indicates a bonding point.

[0086] [ka]

[0087] In formula (6), X 6 This represents an organic group with 2 to 60 carbon atoms and 4 to 6 valent values, Y 6 This represents a divalent to hexavalent organic group with 2 to 70 carbon atoms, (COOR 6 ) is X 6 A substituent located in a position where it can form an imide ring with an amide group that bonds to it, R 6 R represents a hydrogen atom or an organic group with 1 to 5 carbon atoms. 7 R represents a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms, 8 R represents a carboxyl group, a hydroxyl group, or a monovalent organic group having an ethylenically unsaturated bond with 3 to 30 carbon atoms. 7 and R 8 At least one of the atoms has an ethylenically unsaturated bond with 3 to 30 carbon atoms, t is an integer from 0 to 2, u is an integer from 0 to 4, 1 ≤ t + u ≤ 6, and * indicates a bond point.

[0088] The photosensitive resin composition of the present invention, by containing component (A3), results in a cured film of the present invention having a low dielectric constant and low dielectric loss tangent.

[0089] In equations (1), (3), and (5), X 1 , X 3 and X 5 This represents a tetravalent organic group with 2 to 60 carbon atoms, and indicates an acidic component residue. Examples of acidic components include tetracarboxylic acids, tetracarboxylic dianhydrides, or tetracarboxylic diester dichlorides.

[0090] Y 1 , Y 3 and Y 5 This represents a divalent organic group with 2 to 70 carbon atoms, and indicates an amine residue.

[0091] X 1 and Y 1 At least one of these represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds (hereinafter sometimes abbreviated as "structure (a)"), wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms that may have unsaturated bonds.

[0092] X 3 and Y 3 At least one of these represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds (hereinafter sometimes abbreviated as "structure (a)"), wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms that may have unsaturated bonds.

[0093] X 5 and Y 5 At least one of these represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms that may have unsaturated bonds (hereinafter sometimes abbreviated as "structure (a)"), wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms that may have unsaturated bonds.

[0094] By incorporating such a structure, the cured film obtained by curing the resin composition has high elongation, low dielectric constant, and low dielectric loss tangent.

[0095] Examples of structural (a) include cyclobutyl group, cyclobutenyl group, cyclopentyl group, cyclopentenyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cycloheptenyl group, cyclooctyl group, and cyclooctenyl group. From the viewpoint of thermal stability, cyclohexyl group, cyclohexenyl group, cycloheptyl group, and cycloheptenyl group are preferred.

[0096] Examples of C4-C12 hydrocarbon groups that may have unsaturated bonds include n-butyl group, i-butyl group, t-butyl group, 1-butenyl group, 2-butenyl group, n-pentyl group, i-pentyl group, 1-pentenyl group, 2-pentenyl group, n-hexyl group, i-hexyl group, 1-hexenyl group, 2-hexenyl group, n-heptyl group, i-heptyl group, 1-heptenyl group, 2-heptenyl group, n-octyl group, i-octyl group, 1-octenyl group, 2-octenyl group, nonyl group, 1-nonenyl group, decanyl group, 1-decenyl group, undecanyl group, 1-undecenyl group, dodecanyl group, and 1-dodecenyl group.

[0097] Examples of carboxylic acid compounds that form polyvalent carboxylic acid residues include tetracarboxylic acid, hexacarboxylic acid, and octacarboxylic acid, while examples of amine compounds that form polyvalent amine residues include diamine, triamine, and tetraamine.

[0098] Y having the above structure (a) 1 , Y 3 and Y 5These are derived from residues of diamines, triamines, or derivatives having structure (a). Furthermore, by using amino compounds corresponding to these polyvalent amine residues during polymerization, these polyvalent amine residues can be incorporated into the structural units. As for the polyvalent amine residue having structure (a), from the viewpoint of the reliability of the resulting cured film, the polyvalent amine residue represented by formula (7) is preferred, and the diamine residue represented by formula (8), which does not contain a double bond, is more preferred. The diamine residue represented by formula (9) is particularly preferred from the viewpoint of the economics of the diamine and the elongation of the resulting cured film.

[0099] [ka]

[0100] In formula (7), l represents an integer from 4 to 8, W independently represents one of the structural units represented by formulas (7a), (7b), or (7c), with l W containing two or more structural units of (7c), the sum of the numbers of (7b) and (7c) being between 4 and 8, and m and n independently represent an integer from 3 to 11.

[0101] [ka]

[0102] In general formula (8), e', f', g', and h' are natural numbers, where e'+f'=6 to 17 and g'+h'=8 to 19. The dashed parts represent carbon-carbon single bonds or carbon-carbon double bonds. However, at least one double bond is present in each molecule.

[0103] Specific examples of polyhydric amines having structure (a) include commercially available dimer amines and trimertriamines such as “Versamin®” 551, “Versamin®” 552 (both trade names (manufactured by BASF Ltd.)), “Priamine®” 1071, “Priamine®” 1073, “Priamine®” 1074, and “Priamine®” 1075 (all trade names (manufactured by Croda Japan Co., Ltd.)). Here, “Versamin®” 551 and “Priamine®” 1074 are both dimer amine compounds containing the compound represented by formula (10), and “Versamin®” 552, “Priamine®” 1073, and “Priamine®” 1075 are all dimer amine compounds containing the compound represented by formula (9). "Priamine (registered trademark) 1071" is a mixture of dimer amine and trimer triamine.

[0104] X having the above structure (a) 1 , X 3 and X 5 This is derived from a polyvalent carboxylic acid residue or a derivative thereof having structure (a). Furthermore, by using the acid component corresponding to this polyvalent carboxylic acid residue during polymerization, these acid residues can be incorporated into the structural unit. As for polyvalent carboxylic acid residues having structure (a), the aforementioned Y having structure (a) is... 1 , Y 3 and Y 5 Examples include the residues of the reaction product between the polyvalent amines and trimellitic anhydride chloride, as illustrated above. More specifically, the residues of formula (11) are examples.

[0105] In the aforementioned equation (2), R 1 and R 2 Alternatively, R in equation (4) 3 and R 4 Alternatively, R in equation (6) 7 and R 8 Having an ethylenically unsaturated bond at any of these positions improves heat resistance through crosslinking between resins during curing.

[0106] Known methods for introducing ethylenically unsaturated bonds into a resin include reacting hydroxyl groups and / or carboxyl groups in the resin with a compound having an ethylenically unsaturated double bond group, and polymerizing a resin using a monomer having an ethylenically unsaturated bond. From the viewpoint of reactivity, electrophilic compounds having an ethylenically unsaturated double bond group are preferred as the compound having the ethylenically unsaturated double bond group.

[0107] Examples of electrophilic compounds include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thioketone compounds, acetate compounds, carboxylic acid chlorides, carboxylic acid anhydrides, carboxylic acid active ester compounds, carboxylic acid compounds, alkyl halogenated compounds, alkyl azide compounds, triflate alkyl compounds, mesylate alkyl compounds, tosylate alkyl compounds, or alkyl cyanide compounds. However, from the viewpoint of reactivity and the usability of the compounds, isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds, or carboxylic acid anhydrides are preferred, and isocyanate compounds, epoxy compounds, and carboxylic acid anhydrides are more preferred.

[0108] A small amount of polymerization inhibitor may be used to prevent crosslinking of ethylenically unsaturated bond sites during the reaction. Examples of polymerization inhibitors include phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. The amount of polymerization inhibitor added is preferably such that the phenolic hydroxyl groups of the polymerization inhibitor are between 0.1 mol% and 5 mol% relative to the ethylenically unsaturated bonds of the alcohols.

[0109] Furthermore, from the perspective of improving exposure sensitivity, If the resin (A3) contains structural units represented by formula (2), there are multiple R 1 and R 2 At least one of them is a base represented by formula (12) or formula (13), If the resin (A3) contains structural units represented by formula (4), there are multiple R 3 and R 4 At least one of them is a base represented by formula (12) or formula (13), If the resin (A3) contains structural units represented by formula (6), there are multiple R 7 and R 8 Preferably, at least one of them is a group represented by formula (12) or formula (13).

[0110] [ka]

[0111] In formula (12), R 9 R represents a bonding group denoted as -OCH2CH(OH)-, -OCONH-, -NHCH2CH(OH)-, or -NHCONH-. 10 , R 11 , and R 12 Each of the following represents either a hydrogen atom, a methyl group, an ethyl group, or a propyl group; a represents an integer from 1 to 10; and * represents a bond point.

[0112] Due to the ease of introducing the base into the resin (A3), R 9 -OCONH- and -NHCONH- are preferred.

[0113] [ka]

[0114] In general formula (13), R 13 R indicates a bonding group represented by -OCO- or -NHCO-, 14 , R 15 , and R 16 Each of the following represents either a hydrogen atom, a methyl group, an ethyl group, or a propyl group; b represents an integer from 0 to 10; and * represents a bond point.

[0115] From the perspective of heat resistance of the cured film, R 13 NHCO- is preferred.

[0116] It is preferable that the resin (A3) contains 1 to 30 mol% of one or more resins selected from the group consisting of structural units represented by formulas (1), (3), and (5), relative to 100 mol% of the total structural units of resin (A3), and more preferably 1 to 15 mol%. By keeping it within the above range, it is possible to improve heat resistance while maintaining a low dielectric constant and low dielectric loss tangent.

[0117] In the above equations (1) to (6), X 1 ~X 6 However, it contains one or more selected from the group consisting of a bisphenol A skeleton, a biphenyl skeleton, a hexafluoroisopropylidene skeleton, and residues of an acid anhydride represented by formula (14), or Y 1 ~Y 6 Preferably, it contains one or more selected from the group consisting of a bisphenol A skeleton, a biphenyl skeleton, a hexafluoroisopropylidene skeleton, and a diamine residue represented by formula (15).

[0118] By possessing these structural units, it is possible to impart heat resistance and organic solvent solubility while maintaining a low dielectric constant and low dielectric loss tangent.

[0119] [ka]

[0120] In equation (14), z represents an integer between 6 and 20, and * represents a connection point.

[0121] [ka]

[0122] In equation (15), * indicates a bonding point.

[0123] Examples of carboxylic acid compounds having acid anhydride residues represented by a bisphenol A skeleton, a biphenyl skeleton, or a hexafluoroisopropylidene skeleton 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'-isopropylidene diphenoxy)bis(phthalic acid), 4,4'-(4,4'-isopropylidene diphenoxycarbonyl)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.

[0124] Examples of amino compounds having diamine residues represented by a bisphenol A skeleton, a biphenyl skeleton, or a hexafluoroisopropylidene skeleton 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, and bis(3-amino-4-hydroxy)biphenyl. Examples include phenyl, 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.

[0125] Among these, 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 in general formula (15) are preferred from the viewpoint of solubility in organic solvents, transparency, and low dielectric constant.

[0126] In the above equations (1) to (6), Y 1 ~Y 6 It is even more preferable that the compound contains a diamine residue represented by formula (16).

[0127] The inclusion of these diamine residues allows for a lower dielectric loss tangent and improved heat resistance.

[0128] [ka]

[0129] In formula (16), R 17 and R 18 Each of these independently represents a group selected from a methyl group, a trifluoromethyl group, and a hydroxyl group, and v and w represent integers from 0 to 4.

[0130] Examples of amino compounds containing these diamine residues include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-dimethylbiphenyl-4,4'-diamine, and 3,3'-dihydroxybenzidine.

[0131] X 1 ~X 6 and X 8 ~X 10Other carboxylic acid compounds that can be used as acid residues include, for example, pyromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic 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)thioether, and bis(3,4-dicarboxyphenyl Examples include aromatic tetracarboxylic acids such as ethers, 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, or aliphatic tetracarboxylic acids such as bicyclo[3.1.1.]hepto-2-enetetracarboxylic acid, bicyclo[2.2.2.]octanetetracarboxylic acid, or adamatanetetracarboxylic acid.

[0132] These acids can be used as is, or as acid anhydrides, acid chlorides, or activated esters. Examples of activated ester groups include, but are not limited to, the following structures.

[0133] [ka]

[0134] In the formula, A and D represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, and a nitro group. * indicates a bonding point.

[0135] Furthermore, by using silicon atom-containing tetracarboxylic acids such as dimethylsilane diphthalic acid or 1,3-bis(phthalate)tetramethyldisiloxane, adhesion to the substrate and resistance to oxygen plasma and UV ozone treatment used for cleaning can be improved. It is preferable to use these silicon atom-containing tetracarboxylic acids in an amount of 1 to 30 mol% of the total acid component.

[0136] Y 1 ~Y 6 and Y 8 ~Y 10 Other amine compounds that can be used as amine residues include, for example, aromatic diamines such as m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenoxy)benzenebis(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, and 9,9-bis(3-amino Examples include, but are not limited to, aromatic diamines such as (-4-hydroxyphenyl)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, and 4,4'-diaminodiphenyl sulfide, as well as compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc., having 1 to 10 carbon atoms.

[0137] 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. 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.

[0138] The above-mentioned diamine compounds can be used as is, or as compounds in which the amine moiety has been isocyanated or trimethylsilylated. Alternatively, two or more of these diamine compounds may be used in combination.

[0139] Furthermore, it is preferable that the resin (A1), resin (A2), or resin (A3) has a fluorine component in its structure. Having a fluorine component means that the structure contains an organic group having a fluorine atom, X 1 ~X 6 and X 8 ~X 10 or Y 1 ~Y 6 and Y 8 ~Y 10 It is preferable that one of these contains an organic group having a fluorine atom. Known methods for introducing a fluorine component include polymerizing a monomer having a fluorine atom to obtain a resin, or reacting hydroxyl groups and / or carboxyl groups in the resin with a compound having a fluorine atom.

[0140] Compounds containing a fluorine atom include, specifically, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or compounds in which these aromatic rings are substituted with alkyl or halogen atoms, aromatic acid dianhydrides such as acid dianhydrides having an amide group, and bis(3-amino-4-hydroxyphenyl)hexafluoropropane. Examples include aromatic diamines such as 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc., having 1 to 10 carbon atoms.

[0141] Fluorine has a large atomic radius and has the effect of expanding the free volume, which can lower the relative permittivity and dielectric loss tangent. The amount of organic groups containing fluorine atoms is preferably 30 mol% or more relative to 100 mol% of the total structural units of resin (A1), resin (A2), or resin (A3). Furthermore, to obtain good adhesion to the substrate, the amount of organic groups containing fluorine atoms is preferably 90 mol% or less.

[0142] Furthermore, it is preferable that resin (A1), resin (A2), or resin (A3) has 1 to 25 mol% of phenolic hydroxyl groups per 100 mol% of the total structural units. 1 ~X 6 and X 8 ~X 10 or Y 1 ~Y 6 and Y 8 ~Y 10 Preferably, one of the organic groups has a phenolic hydroxyl group. The phenolic hydroxyl group improves heat resistance through hydrogen bonding interactions and contributes to high mechanical properties and chemical resistance through reaction with the crosslinking agent. While the presence of a polar phenolic hydroxyl group tends to worsen the dielectric loss tangent, if it is 1 to 25 mol% relative to 100 mol% of the total structural units of resin (A1), resin (A2), or resin (A3), it is possible to improve mechanical properties and chemical resistance without worsening the dielectric loss tangent. More preferably, it is 1 to 15 mol%.

[0143] Examples of compounds having a phenolic hydroxyl group include aromatic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or compounds in which the aromatic rings thereof are substituted with alkyl groups or halogen atoms, and acid dianhydrides having an amide group, as well as hydroxyl group-containing diamines such as 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, and bis(3-amino-4-hydroxyphenyl)fluorene, and compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc.

[0144] Furthermore, in order to improve the storage stability of the photosensitive resin composition of the present invention and to exhibit various functions, the main chain ends of components (A1) to (A3) may be encapsulated with an end encapsulant. Examples of end encapsulants include monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. In addition, by encapsulating the ends of the resin with an end encapsulant having a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group, maleimide group, or allyl group, the exposure sensitivity and the mechanical properties of the resulting cured film can be easily adjusted to a desirable range.

[0145] The proportion of end-captive agent introduced is preferably 0.1 mol% to 60 mol%, and particularly preferably 5 mol% to 50 mol%, from the viewpoint of solubility in the developer and mechanical properties of the resulting cured film. Multiple end-captive agents may be reacted to introduce multiple different end groups.

[0146] Known compounds can be used as monoamines for end-capturing agents, but 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 may be used.

[0147] Known compounds can be used as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds, but acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic anhydride, and itaconic anhydride are preferred. Maleic anhydride and itaconic anhydride are particularly preferred. Two or more of these may be used.

[0148] In the present invention, components (A1) to (A3) preferably have a weight-average molecular weight of 5,000 or more and 100,000 or less. By setting the weight-average molecular weight to 5,000 or more in polystyrene terms by GPC (gel permeation chromatography), mechanical properties such as elongation, breaking strength, and elastic modulus after curing can be improved. On the other hand, by setting the weight-average molecular weight to 100,000 or less, developability can be improved. For obtaining mechanical properties, 10,000 or more is more preferable. Furthermore, if components (A1) to (A3) contain two or more types of resins, it is sufficient that the weight-average molecular weight of at least one of them is within the above range.

[0149] The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. The inclusion of (B) a photopolymerization initiator enables pattern processing through exposure and development steps. The (B) photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals upon exposure, but alkylphenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, oxime ester compounds, and benzoic acid ester compounds are preferred due to their excellent sensitivity, stability, and ease of synthesis. Among these, alkylphenone compounds and oxime ester compounds are preferred from the viewpoint of sensitivity, and oxime ester compounds are particularly preferred. Furthermore, in the case of thick films with a processed film thickness of 5 μm or more, phosphine oxide compounds are preferred from the viewpoint of resolution.

[0150] Examples of alkylphenone compounds include α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, α-hydroxyalkylphenone compounds such as 1-hydroxycyclohexyl-phenyl ketone and benzoin, and α-alkoxyalkylphenone compounds such as 4-benzoyl-4-methylphenyl ketone and 2,3-diethoxyacetophenone. Among these, α-aminoalkylphenone compounds are preferred due to their high sensitivity.

[0151] An example of a phosphine oxide compound is 6-trimethylbenzoylphenylphosphine oxide.

[0152] Examples of oxime ester compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(0-acetyloxime),2-octanedione,1-[4-(phenylthio)-2-(O-benzoyloxime)], NCI-831, NCI-930 (all trade names, manufactured by ADEKA Corporation), and “Irgacure®” OXE-03, OXE-04 (all trade names, manufactured by BASF Ltd).

[0153] Examples of aminobenzophenone compounds include 4,4-bis(dimethylamino)benzophenone. Examples of diketone compounds include benzyl. Examples of ketoester compounds include methyl benzoylmate. Examples of benzoic acid ester compounds include o-methyl benzoylbenzoate and p-ethyl dimethylaminobenzoate.

[0154] (B) Other specific examples of photopolymerization initiators include benzophenone, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propanaminonium chloride, anthraquinone, triphenylphosphine, and carbon tetrabrominated.

[0155] (B) As for the content of the photopolymerization initiator, when the sum of components (A1) to (A3) and any compound having two or more ethylenically unsaturated bonds is 100 parts by mass, a content of 0.5 parts by mass to 20 parts by mass is preferred because it provides sufficient sensitivity and suppresses the amount of degassing during thermal curing. Among these, 1.0 part by mass to 10 parts by mass is more preferred.

[0156] The photosensitive resin composition of the present invention may contain a sensitizer for the purpose of enhancing the function of (B) the photopolymerization initiator. By including a sensitizer, it is possible to improve sensitivity and adjust the photosensitive wavelength. 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 derivatives thereof.

[0157] The photosensitive resin composition of the present invention preferably further contains a compound (C) having two or more ethylenically unsaturated bonds and an alicyclic structure (hereinafter sometimes abbreviated as "component (C)"). The inclusion of component (C) improves the crosslinking density during exposure, thereby further improving exposure sensitivity and contributing to a reduction in exposure amount and developer film loss. Component (C) can include a known (meth)acrylate compound containing an alicyclic structure, which can achieve a high level of both low dielectric constant, low dielectric loss tangent, and exposure sensitivity.

[0158] Examples of polyfunctional (meth)acrylates containing an alicyclic structure include dimethylol-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-cyclohexanedimethanol di(meth)acrylate, 5-hydroxy-1,3-adamantanedi(meth)acrylate, and EO-modified hydrogenated bisphenol A di(meth)acrylate.

[0159] The content of component (C) is preferably 5 to 100 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of components (A1) to (A3). When the content is within this range, it is easier to obtain improvements in exposure sensitivity, low dielectric constant, and low dielectric loss tangent.

[0160] The photosensitive resin composition of the present invention may contain, in addition to component (C), known (meth)acrylate compounds.

[0161] 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.

[0162] Other polyfunctional (meth)acrylate compounds include, for example, epoxy (meth)acrylate obtained by reacting a polyfunctional epoxy compound with (meth)acrylic acid. Epoxy (meth)acrylate can be used to improve alkali developability because it adds hydrophilicity. These polyfunctional epoxy compounds are preferred because they have excellent heat resistance and chemical resistance.

[0163] [ka]

[0164] The photosensitive resin composition of the present invention preferably contains a thermal crosslinking agent (D) (hereinafter sometimes abbreviated as "component (D)"). By including component (D), the heat resistance and chemical resistance of the cured film can be improved.

[0165] Examples of thermal crosslinking agents include compounds having an epoxy structure, compounds having a hydroxymethyl structure, and compounds having an alkoxymethyl structure.

[0166] The compounds containing epoxy structures may include known compounds. Examples include, but are not limited to, "Epiclon®" 850-S, "Epiclon®" HP-4032, "Epiclon®" HP-7200 (all trade names, available from Dainippon Ink and Chemicals, Inc.), "Licaresin®" BPO-20E, "Licaresin®" BEO-60E (both trade names, available from Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (both trade names, available from Adeka Corporation).

[0167] The compounds may include known compounds having a hydroxymethyl structure and compounds having an alkoxymethyl structure. For example, DML-PC, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, available from Honshu Chemical Industry Co., Ltd.), "NIKALAC®" MX-290, "NIKALAC®" MX-280, "NIKALAC®" MX-270, "NIKALAC®" MX-279, "NIKALAC®" MW-100LM, "NIKALAC®" MX-750LM (all trade names, available from Sanwa Chemical Co., Ltd.).

[0168] Among these compounds, it is preferable that the compound be selected from TMOM-BPAP, NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, or NIKALAC MX-750LM, from the viewpoint of the heat resistance and chemical resistance of the cured film, as well as storage stability.

[0169] The amount of thermal crosslinking agent added is preferably 1 to 20.0 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of components (A1) to (A3). Within this range, it is possible to improve the chemical resistance and heat resistance of the cured film while maintaining a low dielectric loss tangent.

[0170] The photosensitive resin composition of the present invention may contain an antioxidant. By containing an antioxidant, it is possible to suppress the yellowing of the cured film and the deterioration of mechanical properties such as elongation in the heat treatment in the subsequent process. In addition, since the rust prevention action on the metal material can suppress the oxidation of the metal material, it is preferable.

[0171] As the antioxidant, a hindered phenol-based antioxidant or a hindered amine-based antioxidant is preferable.

[0172] Examples of the hindered phenol-based antioxidant include, but are not limited to, "Irganox (registered trademark)" 245, 3114, 1010, 1098, 1135, 259, 035 (the above are product names, manufactured by BASF Corporation), or 2,6-di(t-butyl)-p-cresol.

[0173] Examples of the hindered amine-based antioxidant include, for example, "TINUVIN (registered trademark)" 144, 292, 765, 123 (the above are product names, manufactured by BASF Corporation).

[0174] Examples of other antioxidants include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, phenothiazine, and 4-methoxyphenol. The addition amount of the antioxidant is preferably 0.1 part by mass or more and 10.0 parts by mass or less, more preferably 0.3 part by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the components (A1) to (A3). When it is within such a range, the developability and the discoloration suppression effect by heat treatment can be appropriately maintained.

[0175] The photosensitive resin composition of the present invention may have a heterocyclic compound containing a nitrogen atom. By having a heterocyclic compound containing a nitrogen atom, high adhesion can be obtained on the substrate of metals that are easily oxidized, such as copper, aluminum, and silver. Although the mechanism is not clear, it is presumed that the metal coordination ability of the nitrogen atom interacts with the metal surface, and the bulkiness of the heterocyclic ring stabilizes the interaction.

[0176] Examples of the heterocyclic compound containing a nitrogen atom include imidazole, pyrazole, indazole, carbazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof.

[0177] From the viewpoint of reactivity with metals and the like, as the heterocyclic compound containing a nitrogen atom, 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, etc. are preferable.

[0178] The addition amount of the heterocyclic compound containing a nitrogen atom is preferably 0.01 part by mass or more and 5.0 parts by mass or less, more preferably 0.05 part by mass or more and 3.0 parts by mass or less, based on 100 parts by mass of the components (A1) to (A3). When it is within such a range, the developability and the stabilizing effect of the base metal can be appropriately maintained.

[0179] 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-dimethylisobutyrate amide, and methoxy-N,N-dimethylpropionamide; 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, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be included.

[0180] The solvent content is preferably 100 parts by mass or more per 100 parts by mass of components (A1) to (A3) in order to dissolve the composition, and preferably 1,500 parts by mass or less in order to form a coating film with a thickness of 1 μm or more.

[0181] Furthermore, in order to enhance adhesion to the substrate, the photosensitive resin composition of the present invention may contain a silane coupling agent as a silicon component, to the extent that it does not impair storage stability. Examples of silane coupling agents include trimethoxyaminopropylsilane, trimethoxycyclohexyl epoxyethylsilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, trimethoxyglycidyloxypropylsilane, tris(trimethoxysilylpropyl) isocyanurate, triethoxyaminopropylsilane, and reaction products of trimethoxyaminopropylsilane with acid anhydrides. The reaction product can be used in the form of an amide acid or in an imidized form. Examples of acid anhydrides to be reacted include succinic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, pyromellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, and 4,4'-oxydiphthalic acid dianhydride. The preferred content of the silane coupling agent is 0.01 to 10 parts by mass per 100 parts by mass of components (A1) to (A3).

[0182] Next, a photosensitive sheet formed on a substrate using the photosensitive resin composition of the present invention will be described.

[0183] The photosensitive sheet of the present invention refers to a sheet-like material that is not completely cured, obtained by applying the photosensitive resin composition of the present invention to a substrate and drying it at a temperature and time within a range that allows the solvent to evaporate, and which is soluble in an organic solvent or an alkaline aqueous solution.

[0184] The substrate is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the substrate and the photosensitive resin composition may be surface-treated with silicone, silane coupling agents, aluminum chelating agents, polyurea, etc., to improve adhesion and release properties. The thickness of the substrate is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 μm. Furthermore, a protective film may be placed on the film surface to protect the film surface of the photosensitive composition obtained by coating. This protects the surface of the photosensitive resin composition from pollutants such as dust and dirt in the atmosphere.

[0185] Methods for applying a photosensitive resin composition to a substrate include rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calender coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, and slit die coater. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, viscosity, etc., but generally, the film thickness after drying is preferably 0.5 μm to 100 μm from the viewpoint of coating film uniformity.

[0186] For drying, ovens, hot plates, infrared radiation, etc., can be used. The drying temperature and drying time should be within a range that allows the solvent to evaporate, and it is preferable to set them appropriately within a range that leaves the photosensitive resin composition uncured or semi-cured. Specifically, it is preferable to dry at a temperature of 40°C to 150°C for 1 minute to several tens of minutes. Alternatively, these temperatures may be combined and gradually increased; for example, heat treatment may be performed at 80°C and 90°C for 2 minutes each.

[0187] Next, the photosensitive resin composition of the present invention, or the cured film obtained by curing the photosensitive sheet, will be described.

[0188] The cured film of the present invention can be obtained by curing a photosensitive resin composition or a photosensitive sheet by heat treatment. The heat treatment temperature can be anywhere from 150°C to 350°C. For example, a certain temperature can be selected and the temperature can be increased in stages, or a certain temperature range can be selected and the temperature can be continuously increased for 5 minutes to 5 hours. As an example, heat treatment can be performed at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but it is more preferably 180°C or higher to allow sufficient curing to proceed. There is no particular upper limit to 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.

[0189] Next, a method for forming a relief pattern on a cured film using the photosensitive resin composition or photosensitive sheet of the present invention will be described.

[0190] The photosensitive resin composition of the present invention is applied to a substrate, or the photosensitive sheet is laminated onto a substrate. Suitable substrates include metal copper plated substrates and silicon wafers, and materials such as ceramics and gallium arsenide are used, but are not limited to these. Application methods include rotary coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the application method, the solid content concentration and viscosity of the composition, but is typically applied to achieve a drying thickness of 0.1 to 150 μm.

[0191] To improve the adhesion between the substrate and the photosensitive resin composition, the substrate can be pre-treated with the aforementioned silane coupling agent. For example, a solution can be prepared by dissolving 0.5 to 20% by mass of the silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Next, the prepared solution is applied to the substrate by spin coating, immersion, spray coating, or steam treatment. In some cases, heat treatment to 50°C to 300°C is then performed to promote the reaction between the substrate and the silane coupling agent.

[0192] Next, the photosensitive resin composition is applied, or the substrate laminated with the photosensitive sheet of the present invention is dried to obtain a photosensitive resin composition film. Drying is preferably carried out using an oven, hot plate, infrared, etc., at a temperature of 50°C to 150°C for 1 minute to several hours. In the case of a photosensitive sheet, the drying process is not necessarily required.

[0193] Next, the photosensitive resin composition film is exposed to light. At this time, exposure may be performed by irradiating it with a chemical beam through a mask having a desired pattern. Chemical beams that can be used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in the present invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

[0194] Next, the exposed photosensitive resin composition film may undergo a post-exposure bake (PEB) step if necessary. The PEB step is preferably carried out using an oven, hot plate, infrared light, etc., at a temperature in the range of 50°C to 150°C for 1 minute to several hours.

[0195] Next, the photosensitive resin film after exposure 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 the good solvent and a poor solvent. For example, preferred good solvents are N-methylpyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, and γ-butyrolactone. Preferred poor solvents are toluene, xylene, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more types of solvents, for example, can be used in combination.

[0196] Also, when the photosensitive resin composition is soluble in an aqueous alkali solution, alkali aqueous solution development may be performed. The developer used for development is one that dissolves and removes the alkali aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkali compound is dissolved. Examples of the alkali compound include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, etc. may be contained alone or in combination of several kinds in these aqueous alkali solutions.

[0197] After development, it is preferable to perform a rinse treatment with an organic solvent or water. When using an organic solvent, in addition to the above developer, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. may be mentioned. When using water, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may also be added to the water for rinse treatment.

[0198] Next, the photosensitive resin film after development is heat-treated. After development, a temperature of 150°C to 350°C is applied to allow the thermal crosslinking reaction to proceed and cure. This heat treatment is carried out for 5 minutes to 5 hours by selecting a certain temperature and increasing the temperature stepwise, or by selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the cure conditions is preferably 170°C or higher, more preferably 180°C or higher in order to sufficiently promote the cure. Also, there is no particular limitation on the upper limit of the cure 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.

[0199] The electronic component or display device of the present invention comprises 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, and passive components such as resistors, capacitors, and inductors. Furthermore, packages that enclose these components to improve their durability, and modules that integrate multiple components, are also included in the category of electronic components. Electronic components using semiconductors are also referred to as semiconductor devices or semiconductor packages. Other examples include display panels and touch sensor panels.

[0200] Specific examples of cured films provided on electronic components or display devices include semiconductor passivation films, semiconductor elements, surface protective films for TFTs (Thin Film Transistors), interlayer insulating films such as interlayer insulating films between rewiring in multilayer wiring for high-density mounting of 2 to 10 layers, insulating films and protective films for touch panel displays, insulating films for organic electroluminescence (EL) elements, planarization films for TFT substrates used to drive display devices using organic EL elements, and on-chip microlenses for solid-state image sensors and planarization films for various displays and solid-state image sensors. However, these applications are not limited to these, and various structures can be adopted. Among these, its use as an interlayer insulating film in multilayer wiring for high-density mounting is preferred.

[0201] Next, an example of the application of the cured film obtained by curing the photosensitive resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings. Figure 1 is an enlarged cross-sectional view of the pad portion of a semiconductor device having bumps according to the present invention. As shown in Figure 1, a passivation film 3 is formed on an aluminum (hereinafter abbreviated as Al) pad 2 for input / output on a silicon wafer 1, and via holes are formed in the passivation film 3. An insulating film 4 is formed on this as a pattern of a cured film obtained by curing the photosensitive resin composition of the present invention, and furthermore, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and metal wiring (Al, Cu, etc.) 6 is formed by electroplating or the like. The metal film 5 is etched around the solder bump 10 to insulate the pads. Barrier metal 8 and solder bump 10 are formed on the insulated pads. The cured film obtained by curing the photosensitive resin composition of the insulating film 7 can be processed into a thick film on a scribe line 9.

[0202] Next, the detailed method for fabricating the semiconductor device is shown in Figure 2. As shown in Figure 2a, Al pads 2 for input / output and a passivation film 3 are formed on a silicon wafer 1, and an insulating film 4 is formed as a pattern of a cured film obtained by curing the photosensitive resin composition of the present invention. Subsequently, as shown in Figure 2b, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pads 2, and as shown in Figure 2c, metal wiring 6 is deposited by a plating method. Next, as shown in Figure 2d', the photosensitive resin composition of the present invention before curing is applied, and an insulating film 7 is formed as a pattern as shown in Figure 2d through a photolithography process. At this time, the photosensitive resin composition of the insulating film 7 before curing undergoes thick film processing at the scribe line 9. When forming a multilayer wiring structure of three or more layers, the above process can be repeated to form each layer.

[0203] Next, as shown in Figures 2e and 2f, the barrier metal 8 and solder bumps 10 are formed. Then, the chips are separated by dicing along the final scribe line 9. If the insulating film 7 does not have a pattern formed along the scribe line 9 or if residue remains, cracks may occur during dicing, affecting the reliability evaluation of the chip. For this reason, being able to provide pattern processing that is excellent for thick film processing, as in the present invention, is very desirable for obtaining high reliability of semiconductor devices.

[0204] The antenna element of the present invention comprises at least one antenna wiring and a cured film of the present invention, wherein the antenna wiring includes at least one type selected from the group consisting of meander loop antennas, coil loop antennas, meander monopole antennas, meander dipole antennas, and microstrip antennas, the area occupied by each antenna portion in the antenna wiring is 1000 mm2 or less, and the cured film is preferably an insulating film that insulates the ground from the antenna wiring.

[0205] Here, an antenna element refers to an electronic component that utilizes passive components such as resistors, inductors, and capacitors to perform the function of transmitting and receiving radio waves. The materials used for antenna wiring are not particularly limited as long as they are conductive, and examples include metallic materials such as copper, gold, silver, platinum, aluminum, molybdenum, and titanium. These may be laminates or alloys of different metals, or composites with organic materials such as polymers. Alternatively, carbon materials such as graphite, graphene, and carbon nanotubes, or conductive polymers may also be used. Among these, copper is preferred due to its excellent cost-effectiveness, conductivity, and stability.

[0206] The antenna element of the present invention will be specifically described with reference to Figure 3. Figure 3 is a schematic diagram of a coplanar-fed microstrip antenna, which is a type of planar antenna. 1a is a cross-sectional view, and 1b is a top view. First, the formation method will be described. The photosensitive resin composition of the present invention is applied to copper foil, pre-baked, or an uncured photosensitive sheet is laminated onto the copper foil. Next, the copper foil is laminated and heat-cured to form a cured film having copper foil on both sides. After that, patterning by the substrate method is performed to obtain an antenna element having an antenna pattern of copper wiring of a microstrip line (MSL) as shown in Figure 3.

[0207] Next, the antenna pattern in Figure 3 will be explained. In 1a, 15 is the ground (entire surface), and 16 is the insulating film that serves as the substrate for the antenna. The upper layers 11-13 show the cross-section of the antenna wiring obtained by the patterning described above. The ground wiring thickness J and antenna wiring thickness K can be any thickness depending on the impedance design, but 2-20 μm is common. In 1b, 11 is the antenna section, 12 is the matching circuit, 13 is the MSL feed line, and 14 is the feed point. To match the impedance of the antenna section 11 and the MSL feed line 13, the length M of the matching circuit 12 is 1 / 4λr (λr = (wavelength of transmitted radio wave) / (dielectric constant of insulating material)). 1 / 2 Furthermore, the width W and length L of the antenna section 11 are designed to be 1 / 2λr in length. The antenna section length L may be less than 1 / 2λr depending on the impedance design. Because the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, it can provide an antenna element with high efficiency and high gain. Also, due to these characteristics, the antenna element using the insulating film in the present invention is suitable as an antenna for high frequencies, and the area of ​​the antenna section (=L×W) is 1000mm². 2 By using the following dimensions, a small antenna element can be formed. In this way, a high-efficiency, high-gain, and compact antenna element for high-frequency applications can be obtained.

[0208] Furthermore, the semiconductor package of the present invention comprises at least a semiconductor element, a redistribution layer, a sealing resin, and an antenna wiring, wherein the antenna wiring includes at least one type selected from the group consisting of meander loop antennas, coil loop antennas, meander monopole antennas, meander dipole antennas, and microstrip antennas, and the area occupied by each antenna portion in the antenna wiring is 1000 mm². 2 The following is preferable, wherein the insulating layer and / or the sealing resin of the rewiring layer comprises the cured film of the present invention, and the sealing resin is located between the ground and the antenna wiring.

[0209] The materials used for antenna wiring are those described in the above description of antenna elements. Semiconductor elements include integrated circuits (RFICs) that process signals transmitted and received by the antenna, and may also include semiconductor elements such as amplifiers and noise filters. From the viewpoint of cost and reliability, the rewiring layer preferably consists of 1 to 3 layers of metal wiring and 1 to 4 layers of insulating layers, but is not limited to this. The insulating layer is preferably the cured film of the present invention. The encapsulating resin is preferably the cured film of the present invention, but if used in the insulating layer of the rewiring layer, there are no restrictions, and any encapsulant can be used; a mixture of epoxy resin and inorganic filler is common.

[0210] This document describes a semiconductor package comprising an IC chip (semiconductor element), a redistribution layer, a sealing resin, and an antenna wiring. Figure 4 is a schematic cross-section of the semiconductor package comprising an IC chip (semiconductor element), redistribution, sealing resin, and an antenna element. A redistribution layer (two copper layers, three insulating film layers) is formed on the electrode pads 202 of the IC chip 201, consisting of copper wiring 209 and an insulating film 210 formed from the cured 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 made from the cured film of the present invention is formed, and copper wiring 209 serving as a ground for the antenna is further formed thereon. A first via wiring 207 connecting the ground 206 and the redistribution layer (copper wiring 209 and insulating film 210) is formed through via holes formed in the first sealing resin 208. A second encapsulating resin 205 made of the cured film of the present invention is formed on a first encapsulating resin 208 and a ground 206, and a planar antenna wiring 204 is formed thereon. A second via wiring 203 connecting the planar antenna wiring 204 and a rewiring layer (copper wiring 209 and insulating film 210) is formed through via holes formed in the first encapsulating resin 208 and the second encapsulating resin 205. The thickness of each layer of the insulating film 210 is preferably 10 to 20 μm, and the thicknesses of the first encapsulating resin and the second encapsulating resin are preferably 50 to 200 μm and 100 to 400 μm, respectively. Since the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, the resulting semiconductor package equipped with the antenna element has high efficiency, high gain, and low transmission loss within the package.

[0211] Furthermore, the antenna element of the present invention is an antenna element obtained by laminating antenna wiring and the cured film of the present invention, wherein the height of the antenna wiring is preferably 50 to 200 μm and the thickness of the cured film is preferably 80 to 300 μm. By laminating the antenna wiring and the cured film, and setting the height of the antenna wiring and the thickness of the cured film within the above ranges, it becomes possible to create a small antenna element that can transmit and receive signals over a wide range. Since the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, it is possible to provide an antenna element with high efficiency and high gain. [Examples]

[0212] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods for each example and comparative example will be described. For evaluation, a photosensitive resin composition (hereinafter referred to as varnish) that had been filtered in advance through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore size of 1 μm was used before curing.

[0213] (1) Molecular weight measurement The weight-average molecular weight (Mw) of components (A1) to (A3) was determined using a Waters 2690-996 GPC (gel permeation chromatography) instrument (manufactured by Waters Japan Ltd.). The measurement was performed using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent, and the weight-average molecular weight (Mw) and degree of dispersion (PDI = Mw / Mn) were calculated in polystyrene equivalent.

[0214] (2) Pattern processability (2)-1 Developability and Sensitivity After spin-coating the varnish onto a silicon wafer using a spin coater (1H-360S, manufactured by Mikasa Corporation), the wafer was pre-baked at 120°C for 3 minutes using a hot plate (SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a pre-baked film with a thickness of 11 μm. The obtained pre-baked film was subjected to a 1000 mJ / cm² test using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F, manufactured by Canon Inc.) with a super-high pressure mercury lamp as the light source (g, h, i-line mixed), and a grayscale mask for sensitivity measurement (having a 1:1 line & space pattern of 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12.5 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, and 50 μm, respectively, with areas having transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and 60%) in contact with the film. 2The film was exposed to light. Afterward, it was exposed at 120°C for 3 minutes, then baked, and developed using a coating developer (MARK-7, manufactured by Tokyo Electron Ltd.). It was shower-developed with cyclopentanone (CP) for 30 seconds, followed by rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 15 seconds. If development was excessive or insufficient, the development and rinsing times were adjusted as appropriate.

[0215] After development, the film thickness was measured, and the minimum exposure level at which the film thickness exceeded 95 (with the film thickness at 1000 mJ exposure set to 100) was defined as the optimal exposure level. Furthermore, the residual film ratio, calculated by dividing the film thickness at the optimal exposure level by the pre-baked film thickness, was measured. The sensitivity evaluation criteria are as follows: A: Residual film rate is 90% or higher B: Residual film rate is 80% or more but less than 90% C: Residual film rate is 70% or more but less than 80% D: Residual film rate is 50% or more but less than 70% E: Residual film percentage is less than 50% Furthermore, the exposure amount was measured using an I-line illuminometer. The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., with a refractive index of 1.629. The same method was used for the film thicknesses described below.

[0216] (2)-2 Resolution (2)-1 The minimum pattern size after development at the optimal exposure was measured.

[0217] (3) Measurement of dielectric constant and dielectric loss tangent After applying and pre-baking the varnish onto a 6-inch silicon wafer using the MARK-7 coating and developing system by spin coating to achieve a film thickness of 11 μm after pre-baking at 120°C for 3 minutes, the entire surface was treated with PLA at a rate of 300 mJ / cm². 2The wafers were exposed to light, and then heated to 220°C at a rate of 3.5°C / min using an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, for 1 hour at each temperature. When the temperature dropped below 50°C, the silicon wafers were removed and the cured resin film was peeled off the wafers by immersion in 45% by mass hydrofluoric acid for 1 minute. 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 cavity resonator method in accordance with ASTM D2520 at room temperature (23.0°C) and humidity (45.0% RH). The dielectric properties were measured in five stages as shown in Table 1 below.

[0218] [Table 1]

[0219] (4) Measurement of the glass transition temperature of the cured film after curing A self-supporting cured film was prepared in the same manner as described in "(3) Measurement of Dielectric Constant and Dielectric Loss Tangent" above. This film was cut with a single blade to a width of 0.5 cm and a length of 3.0 cm, and measured using a thermomechanical analyzer (Seiko Instruments, TMA / SS6100) under a nitrogen stream of 80 mL / min, with the temperature raised from 25°C to 400°C at a rate of 10°C / min. The evaluation criteria are as follows: A higher glass transition temperature indicates higher heat resistance of the cured film. A: The glass transition temperature is 200°C or higher. B: Glass transition temperature is between 180°C and 200°C. C: Glass transition temperature is between 150°C and 180°C. D: Glass transition temperature is between 120°C and 150°C. E: The glass transition temperature is less than 120°C.

[0220] (5) Measurement of the elongation at the break point of the cured film after curing. A self-supporting cured film was prepared in the same manner as described in "(3) Measurement of dielectric constant and dielectric loss tangent" above. This film was cut into strips 1.5 cm wide and 9 cm long, and the elongation at the breaking point (%) was measured using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at a tensile speed of 50 mm / min under room temperature of 23.0°C and humidity of 45.0% RH (chuck spacing = 2 cm). Measurements were performed on 10 strips per sample, and the average value of the top 5 highest values ​​was calculated (significant figures = 3 digits).

[0221] (6) Evaluation of chemical resistance Varnish was applied to a silicon wafer using the spin-coating method with a MARK-7 coating and developing system to achieve a film thickness of 10 μm after pre-baking at 120°C for 3 minutes. After pre-baking, the entire coating film was exposed to 300 mJ / cm2 using PLA. The film was then heated to 230°C at a rate of 3.5°C per minute under a nitrogen stream with an oxygen concentration of 20 ppm or less using an inert oven CLH-21CD-S, and the temperature was increased to 230°C for 1 hour. When the temperature dropped below 50°C, the silicon wafer was removed, 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, and the presence or absence of pattern peeling or elution was observed. The results were evaluated as follows: A if there was no pattern peeling and the film thickness change was 5% or less; B if there was no pattern peeling and the film thickness change (indicating swelling or elution) was between 5% and 10%; C if there was no pattern peeling and the film thickness change was between 10% and 20%; D if there was no pattern peeling and the film thickness change was between 20% and 30%; and E if the pattern peeled off and no film remained, or if the film thickness change exceeded 30%.

[0222] The following lists the abbreviations for the compounds used in the synthesis examples and examples. ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride 6FDA: 2,2-Bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride BSAA: 4,4'-(4,4'-isopropylidene diphenoxy)bis(phthalic acid) dianhydride HPMDA: 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride PBOM: 1,1'-(4,4'-oxybenzoyl)diimidazole DAE: 4,4'-diaminodiphenyl ether TFMB: 2,2'-Bis(trifluoromethyl)-4,4'-diaminobiphenyl BAP: 2,2'-bis(3-amino-4-hydroxyphenyl)propane Versamin 551: A dimer amine compound containing the compound represented by formula (10) above (trade name, manufactured by BASF Corporation) (average amine value: 205) Priamine 1075: A dimer amine compound containing the compound represented by formula (9) above (trade name, manufactured by Croda Japan Co., Ltd.) (average amine value: 205) 6FAP: Bis(3-amino-4-hydroxyphenyl)hexafluoropropane BIS-AT-AF: Bis(3-amino-4-methylphenyl)hexafluoropropane DACH: Diaminocyclohexane TAPOB-A: 1,3,5-tris(4-aminophenoxy)benzene) MAP: m-aminophenol MeA: Methacrylic anhydride GMA: Glycidyl methacrylate Karenz MOI: 2-Methacryloyloxyethyl isocyanate (trade name, manufactured by Showa Denko Corporation) NCI-831: Oxime ester-based photopolymerization initiator (trade name, manufactured by ADEKA Corporation) IRGANOX3114: Hindered phenol antioxidant (product name, manufactured by BASF Corporation) DCP-A: Dicyclopentadiene dimethacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) 4G: Tetraethylene glycol dimethacrylate (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.) NIKALAC MW-100LM: A thermal crosslinking agent having an alkoxymethyl structure as shown in the chemical formula below (trade name, manufactured by Sanwa Chemical Co., Ltd.)

[0223] [ka]

[0224] NMP:N-methyl-2-pyrrolidone THF: Tetrahydrofuran CP: Cyclopentanone PGMEA: Propylene glycol methyl ether acetate Polyflow 77: Acrylic surfactant (product name, manufactured by Kyoeisha Chemical Co., Ltd.).

[0225] [Synthesis Example 1: Synthesis of Polyimide Resin (P-1)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 34.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 38.32 g of Versamin 551 (0.140 mol as amino groups) and 6FAP (9.16 g, 0.025 mol) were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. Next, the temperature was raised to 200°C and the mixture was reacted for 3 hours. After cooling to 40°C, 7.71 g (0.05 mol) of MeA was added along with 49.65 g of NMP under a stream of compressed air, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain polyimide resin (P-1) powder.

[0226] [Synthesis Example 2: Synthesis of Polyimide Precursor (P-2)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 4.67 g of 23 NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 38.32 g of Versamin 551 (0.140 mol as amino groups) and 6FAP (9.16 g, 0.025 mol) were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. Subsequently, a solution of 21.45 g (0.180 mol) of N,N-dimethylformamide dimethylacetal (manufactured by Mitsubishi Rayon Co., Ltd.), diluted with 20 g of NMP, was added dropwise over 10 minutes. After addition, the mixture was stirred at 60°C for 3 hours. The mixture was then cooled to 40°C, and under compressed air, 7.71 g (0.05 mol) of MeA was added along with 29.65 g of NMP, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days to obtain polyimide resin (P-2) powder.

[0227] [Synthesis Example 3: Synthesis of Polybenzoxazole Precursor (P-3)] Under a stream of dry nitrogen, 22.93 g (0.100 mol) of PBOM was dissolved in 4.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 85°C for 15 minutes. Then, 38.32 g of Versamin 551 (0.140 mol as amino groups) and 9.16 g (0.025 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 85°C for 3 hours. After cooling to 40°C, 7.71 g (0.05 mol) of MeA was added along with 9.65 g of NMP under a stream of compressed air, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain a polybenzoxazole precursor (P-3) powder.

[0228] [Synthesis Example 4: Synthesis of Polybenzoxazole Resin (P-4)] Under a stream of dry nitrogen, 22.93 g (0.100 mol) of PBOM was dissolved in 4.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 85°C for 15 minutes. Then, 19.16 g of Versamin 551 (0.070 mol as amino groups) and 21.98 g (0.060 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 85°C for 3 hours. Next, the temperature was raised to 200°C and the mixture was reacted for 3 hours. Afterward, the mixture was cooled to 40°C, and under a stream of compressed air, 7.71 g (0.05 mol) of MeA was added along with 29.65 g of NMP, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain polybenzoxazole resin (P-4) powder.

[0229] [Synthesis Example 5: Synthesis of Polyimide Resin (P-5)] Polyimide resin (P-5) was obtained by following the same procedure as in Synthesis Example 1, except that Versamin 551 was replaced with Priamine 1075.

[0230] [Synthesis Example 6: Synthesis of Polyimide Resin (P-6)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 34.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 37.38 g of Priamine 1075 (0.140 mol as amino groups) and 9.16 g (0.025 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. Next, the temperature was raised to 200°C and the mixture was reacted for 3 hours. After cooling to 40°C, under a stream of compressed air, 7.11 g (0.05 mol) of GMA and 0.51 g (0.005 mol) of triethylamine were added along with 49.65 g of NMP, and the mixture was reacted at 90°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain polyimide resin (P-6) powder.

[0231] [Synthesis Example 7: Synthesis of Polyimide Resin (P-7)] Except for replacing MeA with kallenz MOI in Synthesis Example 1, the procedure was carried out in the same manner as in Synthesis Example 1 to obtain polyimide resin (P-7).

[0232] [Synthesis Example 8: Synthesis of the diamine compound TAPOB-A] Under a stream of dry nitrogen, 15.42 g (0.100 mol) of MeA and 221 g of THF were added to a 300 ml round-bottom flask and mixed. 39.95 g (0.100 mol) of TAPOB dissolved in 20 g of NMP was added dropwise. After 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 solution were added to a separatory funnel, and the extraction procedure was performed twice. 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%).

[0233] [ka]

[0234] [Synthesis Example 9: Synthesis of Polyimide Precursor (P-8)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 34.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 38.32 g of Priamine 1075 (0.140 mol as amino groups) and 11.69 g (0.025 mol) of TAPOB-A were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. Subsequently, a solution of 21.45 g (0.180 mol) of N,N-dimethylformamide dimethylacetal (manufactured by Mitsubishi Rayon Co., Ltd.) diluted with 20 g of NMP was added dropwise over 10 minutes. After addition, the mixture was stirred at 60°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain a polyimide precursor (P-8) powder.

[0235] [Synthesis Example 10: Synthesis of Polyimide Resin (P-9)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 4.67 g of 23 NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 19.16 g of Priamine 1075 (0.07 mol as amino groups), 7.01 g (0.035 mol) of DAE, and 9.16 g (0.025 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. The temperature was then raised to 200°C and the mixture was reacted for 3 hours. Afterward, the mixture was cooled to 40°C, and under a stream of compressed air, 7.76 g (0.05 mol) of Karenz MOI was added along with 49.65 g of NMP, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain polyimide resin (P-9) powder.

[0236] [Synthesis Examples 11-15: Synthesis of Polyimide Resins (P-10)-(P-14)] Polyimide resins (P-10) to (P-14) were synthesized in the same manner as in Synthesis Example 10, using the molar ratios shown in Table 2 below.

[0237] [Synthesis Example 16: Synthesis of Polyimide Resin (P-15)] The procedure was carried out in the same manner as in Synthesis Example 13, except that 6FAP was replaced with BAP, to obtain polyimide resin (P-15).

[0238] [Synthesis Example 17: Synthesis of Polyimide Resin (P-16)] Under a stream of dry nitrogen, 52.05 g (0.100 mol) of BSAA was dissolved in 34.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 8.21 g of Priamine 1075 (0.030 mol as amino groups), 11.01 g (0.055 mol) of DAE, and 9.16 g (0.025 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. The temperature was then raised to 200°C and the mixture was reacted for 3 hours. Afterward, the mixture was cooled to 40°C, and under a stream of compressed air, 7.76 g (0.05 mol) of Karenz MOI was added along with 49.65 g of NMP, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain polyimide resin (P-16) powder.

[0239] [Synthesis Example 18: Synthesis of Polyimide Resin (P-17)] Except for changing BSAA in Synthesis Example 17 to 6FDA, the procedure was carried out in the same manner as in Synthesis Example 16 to obtain polyimide resin (P-17).

[0240] [Synthesis Example 19: Synthesis of Polyimide Resin (P-18)] Except for changing BSAA in Synthesis Example 17 to HPMDA, the procedure was carried out in the same manner as in Synthesis Example 16 to obtain polyimide resin (P-18).

[0241] [Synthesis Example 20: Synthesis of Polyimide Resin (P-19)] The procedure was carried out in the same manner as in Synthesis Example 13, except that DAE was replaced with DACH, to obtain polyimide resin (P-19).

[0242] [Synthesis Example 21: Synthesis of Polyimide Resin (P-20)] The synthesis was carried out in the same manner as in Synthesis Example 13, except that DAE was changed to TFMB, to obtain polyimide resin (P-20).

[0243] [Synthesis Example 22: Synthesis of Polyimide Resin (P-21)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 34.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 8.21 g of Priamine 1075 (0.015 mol as amino groups), 12.67 g (0.035 mol) of BIS-AT-AF, and 16.48 g (0.045 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. Next, the temperature was raised to 200°C and the mixture was reacted for 3 hours. Afterward, the mixture was cooled to 40°C, and under a stream of compressed air, 15.52 g (0.010 mol) of Karenz MOI was added along with 49.65 g of NMP, and the mixture was reacted at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for three days to obtain polyimide resin (P-21) powder.

[0244] [Synthesis Examples 23-27: Synthesis of Polyimide Resins (P-22)-(P-26)] Polyimide resins (P-22) to (P-26) were synthesized in the same manner as in Synthesis Example 22, using the molar ratios shown in Table 2 below.

[0245] [Synthesis Example 28: Synthesis of Polyimide Resin (P-27)] Under a stream of dry nitrogen, 31.02 g (0.100 mol) of ODPA was dissolved in 34.67 g of NMP at 60°C. 1.09 g (0.010 mol) of MAP was added along with 5 g of NMP, and the mixture was reacted at 60°C for 15 minutes. Then, 38.32 g of Versamin 551 (0.140 mol as amino groups) and 9.16 g (0.025 mol) of 6FAP were added along with 20 g of NMP, and the mixture was reacted at 60°C for 2 hours. The temperature was then raised to 200°C and the mixture was reacted for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days to obtain polyimide resin (P-27) powder.

[0246] [Synthesis Example 29: Synthesis of Polyimide Resin (P-28)] The procedure was carried out in the same manner as in Synthesis Example 21, except that the preamine 1075 was replaced with DAE, to obtain polyimide resin (P-28).

[0247] [Example 1] Under a yellow light, 10.00 g of polyimide resin (P-1), 0.5 g of NCI-831, 0.10 g of IRGANOX3114, and 0.30 g of 3-trimethoxysilylphthalamidic acid were dissolved in 18.96 g of NMP, and 0.10 g of 1 mass% EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured using the above evaluation method to determine pattern processability, dielectric constant, dielectric loss tangent, and elongation at fracture.

[0248] [Example 2] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-2.

[0249] [Example 3] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-3.

[0250] [Example 4] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-4.

[0251] [Example 5] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-5.

[0252] [Example 6] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-6.

[0253] [Example 7] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-7.

[0254] [Example 8] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-8.

[0255] [Example 9] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-9.

[0256] [Example 10] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-10.

[0257] [Example 11] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-11.

[0258] [Example 12] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-12.

[0259] [Example 13] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-13.

[0260] [Example 14] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-14.

[0261] [Example 15] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-15.

[0262] [Example 16] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-16.

[0263] [Example 17] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-17.

[0264] [Example 18] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-18.

[0265] [Example 19] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-19.

[0266] [Example 20] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-20.

[0267] [Example 21] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-21.

[0268] [Example 22] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-22.

[0269] [Example 23] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-23.

[0270] [Example 24] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-24.

[0271] [Example 25] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-25.

[0272] [Example 26] The procedure was carried out in the same manner as in Example 1, except that P-1 was replaced with P-26.

[0273] [Example 27] Under a yellow light, 10.00 g of polyimide resin (P-21), 0.5 g of NCI-831, 0.10 g of IRGANOX3114, 0.30 g of 3-trimethoxysilylphthalamidic acid, and 0.5 g of MW-100LM were dissolved in 18.96 g of NMP, and 0.10 g of a 1 mass% EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured using the above evaluation method to determine pattern processability, dielectric constant, dielectric loss tangent, and elongation at fracture.

[0274] [Example 28] The procedure was carried out in the same manner as in Example 27, except that P-21 was replaced with P-23.

[0275] [Example 29] The procedure was carried out in the same manner as in Example 27, except that P-21 was replaced with P-25.

[0276] [Example 30] Under a 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 IRGANOX3114, and 0.30 g of 3-trimethoxysilylphthalamidic acid were dissolved in 18.96 g of NMP, and 0.10 g of 1 mass% EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured using the above evaluation method to determine pattern processability, dielectric constant, dielectric loss tangent, and elongation at fracture.

[0277] [Example 31] The procedure was carried out in the same manner as in Example 30, except that 4G was replaced with DCP-A.

[0278] [Comparative Example 1] P-1 to P- 27 The procedure was carried out in the same manner as in Example 1, except that a substitute was made.

[0279] [Comparative Example 2] P-1 to P- 28 The procedure was carried out in the same manner as in Example 1, except that a substitute was made.

[0280] The compositions and evaluation results of the examples and comparative examples are shown in Tables 2 to 4 below.

[0281] [Table 2]

[0282] [Table 3-1]

[0283] [Table 3-2]

[0284] [Table 4-1]

[0285] [Table 4-2] [Explanation of symbols]

[0286] 1 silicon wafer 2 Al pads 3 Passivation membrane 4. Insulating film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.) 7. Insulating film 8 Barrier Metal 9 Scribe lines 10 Solder Bumps 11 Antenna section 12 Matching Circuit 13 MSL power supply lines 14 Power supply point 15 Grand 16 Insulating film J Ground wiring thickness K Antenna wiring thickness M Matching circuit length L Antenna section length W Antenna section width 201 IC chips 202 Electrode Pads 203 Second via wiring 204 Planar antenna wiring 205 Second sealing resin 206 Grand 207 First via wiring 208 First sealing resin 209 Copper Wiring 210 insulating film 211 Barrier Metal 212 Solder Bump

Claims

1. A resin (A3) containing one or more structural units selected from the group consisting of structural units represented by formulas (1), (3), and (5), and further containing one or more structural units selected from the group consisting of structural units represented by formulas (2), (4), and (6), and a photopolymerization initiator (B), For every 100 mol% of the total structural units of resin (A3), one or more structural units selected from the group consisting of structural units represented by formulas (1), (3), and (5) are included in an amount of 1 to 30 mol%, A photosensitive resin composition in which Y1 in formula (1), Y3 in formula (3), and Y5 in formula (5) are residues of a polyvalent amine represented by formula (7). 【Chemistry 1】 In formula (1), X １ This represents a tetravalent organic group with 6 to 60 carbon atoms, Y １ This represents a divalent organic group with 6 to 70 carbon atoms, X １ and Y １ At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bond site. 【Chemistry 2】 In formula (2), X ２ represents a tetravalent to hexavalent organic group having 6 to 60 carbon atoms, Y ２ represents a divalent to hexavalent organic group having 6 to 70 carbon atoms, and a plurality of R １ and R ２ each independently represent a monovalent organic group having 3 to 30 carbon atoms and having a carboxyl group, a hydroxyl group, or an ethylenic unsaturated bond, and at least one of R １ and R ２ represents a monovalent organic group having 3 to 30 carbon atoms and having an ethylenic unsaturated bond, p represents an integer of 0 to 2, q represents an integer of 0 to 4, 1 ≦ p + q ≦ 6, and * represents a bonding point. 【Transformation 3】 In formula (3), X ３ This represents a tetravalent organic group with 6 to 60 carbon atoms, Y ３ This represents a divalent organic group with 6 to 70 carbon atoms, X ３ and Y ３ At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the cycloaliphatic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bond site. 【Chemistry 4】 In formula (4), X ４ This represents an organic group with 6 to 60 carbon atoms and 4 to 6 valent values, Y ４ This represents a divalent to hexavalent organic group with 6 to 70 carbon atoms, and multiple R ３ and R ４ These may be the same or different, and represent a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond, R ３ and R ４ At least one of the elements represents a monovalent organic group having 3 to 30 carbon atoms and possessing an ethylenically unsaturated bond, r is an integer from 0 to 2, s is an integer from 0 to 4, 1 ≤ r + s ≤ 6, and * represents a bond point. 【Transformation 5】 In formula (5), X ５ This represents a tetravalent organic group with 6 to 60 carbon atoms, Y ５ This represents a divalent organic group with 6 to 70 carbon atoms, X ５ and Y ５ At least one of these represents a polycarboxylic acid residue and / or a polyamine residue having a structure of a cycloaliphatic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, and in the structure of the cycloaliphatic hydrocarbon, at least four or more hydrogen atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, (COOR ５ ) is X ５ A substituent that can bond with an amide group and form an imide ring, R ５ * indicates a hydrogen atom or an organic group having 1 to 5 carbon atoms, and * indicates a bonding point. 【Transformation 6】 In formula (6), X ６ This represents an organic group with 6 to 60 carbon atoms and 4 to 6 valent values, Y ６ This represents a divalent to hexavalent organic group with 6 to 70 carbon atoms, (COOR ６ ) is X ６ A substituent that can bond with an amide group and form an imide ring, R ６ R represents a hydrogen atom or an organic group having 1 to 5 carbon atoms. ７ R represents a hydroxyl group or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond. ８ R represents a carboxyl group, a hydroxyl group, or a monovalent organic group having 3 to 30 carbon atoms and an ethylenically unsaturated bond. ７ and R ８ At least one of the atoms has an ethylenically unsaturated bond with 3 to 30 carbon atoms, t is an integer from 0 to 2, u is an integer from 0 to 4, 1 ≤ t + u ≤ 6, and * indicates a bond point. 【Transformation 7】 In formula (7), l represents an integer from 4 to 8, W independently represents one of the structural units represented by formulas (7a), (7b), or (7c), with l W containing two or more structural units of (7c), the sum of the numbers of (7b) and (7c) being between 4 and 8, and m and n independently represent an integer from 3 to 11.

2. A resin (A3) containing one or more structural units selected from the group consisting of structural units represented by formulas (1), (3), and (5), and further containing one or more structural units selected from the group consisting of structural units represented by formulas (2), (4), and (6), and a photopolymerization initiator (B), For every 100 mol% of the total structural units of resin (A3), one or more structural units selected from the group consisting of structural units represented by formulas (1), (3), and (5) are included in an amount of 1 to 30 mol%, A photosensitive resin composition in which Y1 in formula (1), Y3 in formula (3), and Y5 in formula (5) are residues of a diamine represented by formula (9). 【Transformation 8】 In formula (1), X1 represents a tetravalent organic group having 6 to 60 carbon atoms, Y1 represents a divalent organic group having 6 to 70 carbon atoms, and at least one of X1 and Y1 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bonding site. 【Chemistry 9】 In formula (2), X2 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y2 represents a 2-6 valent organic group having 6 to 70 carbon atoms, multiple R1 and R2 each independently represent a 3-30 valent monovalent organic group having a carboxyl group, a hydroxyl group, or an ethylenically unsaturated bond, at least one of R1 and R2 represents a 3-30 valent monovalent organic group having an ethylenically 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 bond point. 【Chemistry 10】 In formula (3), X3 represents a tetravalent organic group having 6 to 60 carbon atoms, Y3 represents a divalent organic group having 6 to 70 carbon atoms, and at least one of X3 and Y3 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bonding site. 【Chemistry 11】 In formula (4), X4 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y4 represents a 2-6 valent organic group having 6 to 70 carbon atoms, multiple R3 and R4 may be the same or different, and each represents a 3-30 valent monovalent organic group having a carboxyl group, a hydroxyl group, or an ethylenically unsaturated bond, at least one of R3 and R4 represents a 3-30 valent monovalent organic group having an ethylenically 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 bond point. 【Chemistry 12】 In formula (5), X 5 represents a tetravalent organic group having 6 to 60 carbon atoms, Y 5 represents a divalent organic group having 6 to 70 carbon atoms, at least one of X 5 and Y 5 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, in which at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, (COOR 5) is a substituent located in a position that can form an imide ring with an amide group bonded to X 5, R 5 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms, and * represents a bonding site. 【Chemistry 13】 In formula (6), X 6 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y 6 represents a 2-6 valent organic group having 6 to 70 carbon atoms, (COOR 6) is a substituent in a position that can form an imide ring with an amide group bonded to X 6, R 6 represents a hydrogen atom or an organic group having 1 to 5 carbon atoms, R 7 represents a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond between 3 and 30 carbon atoms, R 8 represents a carboxyl group, a hydroxyl group, or a monovalent organic group having an ethylenically unsaturated bond between 3 and 30 carbon atoms, at least one of R 7 and R 8 has an ethylenically unsaturated bond between 3 and 30 carbon atoms, t represents an integer between 0 and 2, u represents an integer between 0 and 4, 1 ≤ t + u ≤ 6, and * represents a bond point. 【Chemistry 14】

3. A resin (A3) containing one or more structural units selected from the group consisting of structural units represented by formula (1) and formula (3), and further containing one or more structural units selected from the group consisting of structural units represented by formula (2) and formula (4), and a photopolymerization initiator (B), A photosensitive resin composition in which Y1 in formula (1) and Y3 in formula (3) are residues of a polyvalent amine represented by formula (7). 【Chemistry 15】 In formula (1), X1 represents a tetravalent organic group having 6 to 60 carbon atoms, Y1 represents a divalent organic group having 6 to 70 carbon atoms, and at least one of X1 and Y1 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bonding site. 【Chemistry 16】 In formula (2), X2 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y2 represents a 2-6 valent organic group having 6 to 70 carbon atoms, multiple R1 and R2 each independently represent a 3-30 valent monovalent organic group having a carboxyl group, a hydroxyl group, or an ethylenically unsaturated bond, at least one of R1 and R2 represents a 3-30 valent monovalent organic group having an ethylenically 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 bond point. 【Chemistry 17】 In formula (3), X3 represents a tetravalent organic group having 6 to 60 carbon atoms, Y3 represents a divalent organic group having 6 to 70 carbon atoms, and at least one of X3 and Y3 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bonding site. [Chemistry 18] In formula (4), X4 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y4 represents a 2-6 valent organic group having 6 to 70 carbon atoms, multiple R3 and R4 may be the same or different, and each represents a 3-30 valent monovalent organic group having a carboxyl group, a hydroxyl group, or an ethylenically unsaturated bond, at least one of R3 and R4 represents a 3-30 valent monovalent organic group having an ethylenically 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 bond point. 【Chemistry 19】 In formula (7), l represents an integer from 4 to 8, W independently represents one of the structural units represented by formulas (7a), (7b), or (7c), with l W containing two or more structural units of (7c), the sum of the numbers of (7b) and (7c) being between 4 and 8, and m and n independently represent an integer from 3 to 11.

4. A resin (A3) containing one or more structural units selected from the group consisting of structural units represented by formula (1) and formula (3), and further containing one or more structural units selected from the group consisting of structural units represented by formula (2) and formula (4), and a photopolymerization initiator (B), A photosensitive resin composition in which Y1 in formula (1) and Y3 in formula (3) are residues of a diamine represented by formula (9). 【Chemistry 20】 In formula (1), X1 represents a tetravalent organic group having 6 to 60 carbon atoms, Y1 represents a divalent organic group having 6 to 70 carbon atoms, and at least one of X1 and Y1 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bonding site. 【Chemistry 21】 In formula (2), X2 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y2 represents a 2-6 valent organic group having 6 to 70 carbon atoms, multiple R1 and R2 each independently represent a 3-30 valent monovalent organic group having a carboxyl group, a hydroxyl group, or an ethylenically unsaturated bond, at least one of R1 and R2 represents a 3-30 valent monovalent organic group having an ethylenically 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 bond point. 【Chemistry 22】 In formula (3), X3 represents a tetravalent organic group having 6 to 60 carbon atoms, Y3 represents a divalent organic group having 6 to 70 carbon atoms, and at least one of X3 and Y3 represents a polyvalent carboxylic acid residue and / or a polyvalent amine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which may have unsaturated bonds, wherein at least four hydrogen atoms in the structure of the alicyclic hydrocarbon are substituted with a hydrocarbon group having 4 to 12 carbon atoms which may have unsaturated bonds, and * indicates a bonding site. 【Chemistry 23】 In formula (4), X4 represents a 4-6 valent organic group having 6 to 60 carbon atoms, Y4 represents a 2-6 valent organic group having 6 to 70 carbon atoms, multiple R3 and R4 may be the same or different, and each represents a 3-30 valent monovalent organic group having a carboxyl group, a hydroxyl group, or an ethylenically unsaturated bond, at least one of R3 and R4 represents a 3-30 valent monovalent organic group having an ethylenically 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 bond point. 【Chemistry 24】

5. If 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 base represented by formula (12) or formula (13), If the resin (A3) contains structural units represented by formula (4), there are multiple R ３ and R ４ At least one of them is a base represented by formula (12) or formula (13), If the above formula (6) exists and the resin (A3) contains a structural unit represented by formula (6), then there are multiple R ７ and R ８ At least one of them is a base represented by formula (12) or formula (13), A photosensitive resin composition according to any one of claims 1 to 4. 【Chemistry 25】 In formula (12), R ９ ha-OCH ２ CH(OH)-, -OCONH-, -NHCH ２ The bond group is represented by CH(OH)- or -NHCONH-, R １０ , R １１ , and R １２ Each of the following represents either a hydrogen atom, a methyl group, an ethyl group, or a propyl group; a represents an integer from 1 to 10; and * represents a bond point. 【Chemistry 26】 In formula (13), R １３ represents a bonding group denoted by -OCO- or -NHCO-, R １４ , R １５ , and R １６ Each of the following represents either a hydrogen atom, a methyl group, an ethyl group, or a propyl group; b represents an integer from 0 to 10; and * represents a bond point.

6. A photosensitive resin composition according to any one of claims 3 to 5, wherein, with respect to 100 mol% of the total structural units of resin (A3), one or more structural units selected from the group consisting of structural units represented by formula (1), formula (3), and (if any) formula (5) are contained in an amount of 1 to 30 mol%.

7. In the above formulas (1) to (6), X １ ~X ６ However, it includes one or more selected from the group consisting of a bisphenol A skeleton, a biphenyl skeleton, a hexafluoroisopropylidene skeleton, and residues of an acid anhydride represented by formula (14), Or, Y １ ~Y ６ A photosensitive resin composition according to any one of claims 1 to 6, wherein the component comprises one or more selected from the group consisting of a bisphenol A skeleton, a biphenyl skeleton, a hexafluoroisopropylidene skeleton, and a diamine residue represented by formula (15). 【Chemistry 27】 In equation (14), z represents an integer between 6 and 20, and * represents a connection point. 【Chemistry 28】 In equation (15), * indicates a connection point.

8. In the above formulas (1) to (6), Y １ ~Y ６ The photosensitive resin composition according to any one of claims 1 to 7, wherein any of the following contains a diamine residue represented by formula (16). 【Chemistry 29】 In formula (16), R １７ and R １８ Each of these independently represents a group selected from a methyl group, a trifluoromethyl group, and a hydroxyl group, and v and w represent integers from 0 to 4.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the resin (A3) has a fluorine component in its structure.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the resin (A3) has 1 to 25 mol% of phenolic hydroxyl groups based on 100 mol% of the total structural units.

11. Furthermore, the photosensitive resin composition according to any one of claims 1 to 10 contains two or more ethylenically unsaturated bonds and a compound (C) having an alicyclic structure.

12. Furthermore, the photosensitive resin composition according to any one of claims 1 to 11, further containing a thermal crosslinking agent (D).

13. A photosensitive sheet formed on a substrate using the photosensitive resin composition according to any one of claims 1 to 12.

14. A photosensitive resin composition according to any one of claims 1 to 12, or a photosensitive sheet according to claim 13. A cured film obtained by hardening the material.

15. A photosensitive resin composition according to any one of claims 1 to 12, or a photosensitive sheet according to claim 13. A method for producing a cured film using, A method for producing a cured film, comprising the steps of: applying the photosensitive resin composition onto a substrate or laminating the photosensitive sheet onto a substrate and drying to form a photosensitive resin film; exposing the photosensitive resin film to light; developing the photosensitive resin film after exposure; and heat-treating the photosensitive resin film after development.

16. An electronic component comprising the cured film described in claim 14.

17. An antenna element comprising at least one antenna wiring and the cured film described in claim 14, wherein the antenna wiring includes at least one selected from the group consisting of meander loop antennas, coil loop antennas, meander monopole antennas, meander dipole antennas, and microstrip antennas, and the area occupied by each antenna portion in the antenna wiring is 1000 mm². ２ The following is an antenna element, wherein the cured film is an insulating film that insulates between the ground and the antenna wiring.

18. A semiconductor package comprising at least a semiconductor element, a redistribution layer, a sealing resin, and an antenna wiring, The antenna wiring includes at least one type selected from the group consisting of meander loop antennas, coil loop antennas, meander monopole antennas, meander dipole antennas, and microstrip antennas. The area occupied by each antenna section in the antenna wiring is 1000 mm². ２ A semiconductor package wherein the insulating layer of the redistribution layer and / or the sealing resin comprises the cured film described in claim 14, and the sealing resin is located between the ground and the antenna wiring.

19. An antenna element obtained by laminating antenna wiring and a cured film according to claim 14, wherein the height of the antenna wiring is 50 to 200 μm and the thickness of the cured film is 80 to 300 μm.

20. A display device comprising the cured film described in claim 14.

Images