Photosensitive resin composition, photosensitive sheet, cured film, method for producing cured film, interlayer insulating film, and electronic component

Abstract

The present invention aims to provide a photosensitive resin composition having good pattern processing properties, and a cured film obtained by curing the same, having a low dielectric constant, a low dielectric loss tangent, and a high elongation. The present invention is a photosensitive resin composition containing (A) a polyimide precursor containing a polycarboxylic acid residue and / or a polyamine residue having a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which can have an unsaturated bond, in which at least 4 or more hydrogen atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms which can have an unsaturated bond, and (B) a photopolymerization initiator.

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive resin composition, a photosensitive sheet, a cured film, a method for manufacturing a cured film, an interlayer insulating film, and an electronic component. More specifically, it relates to a photosensitive resin composition suitable for a surface protective film for an electronic component such as a semiconductor element, an interlayer insulating film, an insulating layer for an organic electroluminescent element, and the like. BACKGROUND

[0002] As a representative material of a surface protective film for a semiconductor element, an interlayer insulating film, an insulating layer for an organic electrolytic element, a planarization film for a TFT substrate, a polyimide-based resin having excellent heat resistance, electrical insulation, and the like can be mentioned. Further, in order to improve productivity, a photosensitive polyimide and a precursor thereof having a negative photosensitivity have also been studied.

[0003] In recent years, with the expansion of the use of semiconductors and the improvement of performance, efforts have been made to reduce costs and increase integration due to the efficiency of the manufacturing process. Therefore, semiconductor devices in which a plurality of metal rewiring layers are formed have attracted attention. For such an insulating film for a multilayer metal rewiring layer, resistance to cracking accompanying multilayerization, low dielectric constantization accompanying high integration, and the like are required. Further, in the use of high-frequency communication devices for high-speed wireless communication, in order to reduce transmission loss, the insulating film is required to have a low dielectric loss tangent.

[0004] As a means to improve the cracking resistance, a method of introducing a soft oxyalkylene skeleton into the main chain of a polyimide has been proposed (Patent Document 1). As a means to low dielectric constantization, a method of using an alicyclic polyimide has been proposed (Patent Document 2). As a means to low dielectric loss tangent, a soluble polyimide using a dimer diamine has been proposed as an adhesive layer (Patent Document 3).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-208360

[0008] Patent Document 2: Japanese Patent Application Publication No. 2009-186861

[0009] Patent Document 3: Japanese Patent Application Publication No. 2018-203959 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] In the case where the prior art is applied as a multilayer wiring insulating film for a high-frequency communication device for high-speed wireless communication, for example, in Patent Literature 1, the dielectric constant is poor because of the oxyalkylene group that increases water absorption, in Patent Literature 2, the crack resistance is insufficient because of the low elongation, and in Patent Literature 3, there is a problem that the exposure sensitivity is not sufficient.

[0012] Means for solving the problem

[0013] To solve the above problem, the present application relates to the following solutions.

[0014] A photosensitive resin composition contains (A) a polyimide precursor including a resin having a structural unit represented by General Formula (11), and (B) a photopolymerization initiator.

[0015]

[0016] In General Formula (11), X 4 represents a 4- to 6-valent organic group, Y 4 represents a 2- to 6-valent organic group. At least any one of X 4 and Y 4 represents an organic group including one or more alicyclic structures and a plurality of hydrocarbon structures having 4 or more carbon atoms. A plurality of R 8 each independently represents a 1-valent organic group having an ethylenic unsaturated bond or a hydrogen atom. At least one of a plurality of R 8 is a 1-valent organic group having an ethylenic unsaturated bond. X represents an integer of 2 to 4. A plurality of R 9 each independently represents a carboxyl group, a hydroxyl group, or a 1-valent organic group having an ethylenic unsaturated bond. Y represents an integer of 0 to 4. * represents a bonding point.

[0017] Other solutions of the present application are described below.

[0018] A photosensitive resin composition contains (A) a polyimide precursor including a resin having a structural unit represented by General Formula (1), and (B) a photopolymerization initiator.

[0019]

[0020] In General Formula (1), X 1 represents a 4- to 6-valent organic group, Y 1 represents a 2- to 6-valent organic group. At least any one of X 1 and Y 1 has the structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms that can 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 that can have an unsaturated bond. A plurality of R1 which can be the same or different, represent a monovalent organic group having an ethylenically unsaturated bond or a hydrogen atom. Of these, not all of R 1 are hydrogen atoms. p represents an integer of 2 to 4. Multiple R 2 which can be the same or different, represent a carboxyl group, a hydroxyl group, or a monovalent organic group having an ethylenically unsaturated bond. q represents an integer of 0 to 4. * represents a bonding point.

[0021] Effects of the Invention

[0022] The photosensitive resin composition of the present application has excellent exposure sensitivity. Furthermore, the elongation, low dielectric constant, and low dielectric loss tangent of the cured film obtained by curing the same are excellent. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 is a drawing showing an enlarged cross section of a pad portion of a semiconductor device having a bump.

[0024] Figure 2 is a drawing showing a detailed manufacturing method of a semiconductor device having a bump.

[0025] Figure 3 is a schematic view of a coplanar-fed type microstrip antenna.

[0026] Figure 4 is a schematic view of a cross section relating to a semiconductor package provided with an IC chip (semiconductor element), a rewiring layer, a sealing resin, and an antenna element. DETAILED DESCRIPTION

[0027] The present application provides a photosensitive resin composition containing (A) a polyimide precursor, and (B) a photopolymerization initiator. Hereinafter, each component will be described.

[0028] The photosensitive resin composition of the present application contains (A) a polyimide precursor (hereinafter, sometimes abbreviated as "(A) component"). By including the (A) component, the cured film obtained by curing the photosensitive composition becomes low in dielectric constant and dielectric loss tangent. The (A) polyimide precursor contains a structural unit of the following general formula (11).

[0029]

[0030] In the general formula (11), X 4 represents a 4- to 6-valent organic group, and Y 4 represents a 2- to 6-valent organic group. Of these, at least either one of X 4 and Y 4 represents an organic group containing one or more alicyclic structures and a plurality of hydrocarbon structures having 4 or more carbon atoms. Multiple R 8each independently represents a monovalent organic group having an ethylenically unsaturated bond or a hydrogen atom. Among them, a plurality of R 8 at least one of which is a monovalent organic group having an ethylenically unsaturated bond. x represents an integer of 2 to 4. A plurality of R 9 each independently represents a carboxyl group, a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond. y represents an integer of 0 to 4. * represents a bonding point.

[0031] In other aspects of the present application, the (A) polyimide precursor contains a structure of the following general formula (1).

[0032]

[0033] In the general formula (1), X 1 represents a 4- to 6-valent organic group, Y 1 represents a 2- to 6-valent organic group. Among them, at least either one of X 1 and Y 1 has a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which can 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 can have an unsaturated bond. A plurality of R 1 which can be the same or different, represents a monovalent organic group having an ethylenically unsaturated bond or a hydrogen atom. Among them, not all of R 1 are hydrogen atoms. p represents an integer of 2 to 4. A plurality of R 2 which can be the same or different, represents a carboxyl group, a hydroxyl group or a monovalent organic group having an ethylenically unsaturated bond. q represents an integer of 0 to 4. * represents a bonding point.

[0034] In the general formula (1), X 1 represents a 4- to 6-valent organic group, and represents a residue of a polycarboxylic acid. As the polycarboxylic acid, tetra carboxylic acid, tetra carboxylic dianhydride or tetra carboxylic diester dichloride, etc. can be mentioned. Here, in the present specification, in the case of being expressed as "~", unless otherwise specified, it means to include the numbers of the upper limit and the lower limit. Y 1 represents a 2- to 6-valent organic group, and represents a residue of a polyamine. X 1 and Y 1 at least either one of which has a structure of an alicyclic hydrocarbon having 4 to 8 carbon atoms which can have an unsaturated bond (hereinafter, sometimes abbreviated as "structure (a)"). Among them, 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 can have an unsaturated bond.

[0035] That is, there are a case where X 1 represents a polycarboxylic acid residue having the structure (a), a case where Y 1 represents a polyamine residue having the structure (a), a case where X 1 and Y1 respectively. By containing such structures, the cured film obtained by curing the resin composition has high elongation, low dielectric constant, and low dielectric loss tangent.

[0036] With respect to the above structure (a), specific examples are described. As the alicyclic hydrocarbon having 4 to 8 carbon atoms which can have an unsaturated bond, cyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, and the like can be given. Among them, from the viewpoint of thermal stability, cyclohexyl, cyclohexenyl, cycloheptyl, and cycloheptenyl are preferred.

[0037] As the hydrocarbon group having 4 to 12 carbon atoms which can have an unsaturated bond, n-butyl, iso-butyl, t-butyl, 1-butenyl, 2-butenyl, n-pentyl, iso-pentyl, 1-pentenyl, 2-pentenyl, n-hexyl, iso-hexyl, 1-hexenyl, 2-hexenyl, n-heptyl, iso-heptyl, 1-heptenyl, 2-heptenyl, n-octyl, iso-octyl, 1-octenyl, 2-octenyl, nonyl, 1-nonenyl, decyl, 1-decenyl, undecyl, 1-undecenyl, dodecyl, 1-dodecenyl, and the like can be given.

[0038] The above Y having structure (a) is 1 is a polyamine residue, and is a residue derived from a diamine, a triamine, or a derivative thereof having structure (a). Further, by using an amino compound corresponding to the polyamine residue at the time of polymerization, it is possible to cause the structural unit to contain these polyamine residues. As the polyamine having structure (a), a polyamine represented by the following general formula (2) or the following general formula (3) can be given. Among them, from the viewpoint of reliability of the obtained cured film, the polyamine given in general formula (2) which does not contain a double bond is preferred. Further, the polyamine represented by the following formula (4) is more preferred from the viewpoints of economy, elongation of the obtained cured film, and the like.

[0039]

[0040] In general formula (2), m represents any one of integers from 4 to 8. Each of W independently represents any one of the structural units represented by general formulae (2a), (2b), and (2c). Among the m W's, 2 or more of the structural units of (2c) are contained, and the sum of the numbers of (2b) and (2c) is 4 or more and 8 or less. Each of n or o independently represents any one of integers from 3 to 11.

[0041]

[0042] In General Formula (3), e, f, g, h are natural numbers, e + f = 6 to 17, and g + h = 8 to 19. The wavy line portion indicates a carbon-carbon single bond or a carbon-carbon double bond. Of these, at least one of the 1 molecule indicates a double bond.

[0043]

[0044] As specific examples of the polyamine having structure (a), as a dimer diamine, a trimer triamine, commercially available products such as "Versamine 551", "Versamine 552" (both, trade name (manufactured by BASF Corporation)), "Primamine 1071", "Primamine 1073", "Primamine 1074", "Primamine 1075" (all, trade name (manufactured by Clariant Japan K.K.)) can be given. Here, "Versamine 551", "Primamine 1074" are both dimer diamine compounds containing a compound represented by the following formula (5), and "Versamine 552", "Primamine 1073", "Primamine 1075" are all dimer diamine compounds containing a compound represented by the above formula (4). "Primamine 1071" is a mixture of a dimer diamine and a trimer triamine.

[0045]

[0046] The above X having structure (a) 1 is a polycarboxylic acid residue, and is a residue derived from a polycarboxylic acid residue or a derivative thereof having structure (a). As a polycarboxylic acid compound which becomes a polycarboxylic acid residue, a tetracarboxylic acid, a hexacarboxylic acid, and an octacarboxylic acid can be given. Furthermore, by using a polycarboxylic acid component corresponding to the polycarboxylic acid residue at the time of polymerization, it is possible to make the structural unit contain these polycarboxylic acid residues. As a polycarboxylic acid having structure (a), a polyamine of the kind exemplified in the above Y having structure (a) 1 can be given. More specifically, a reactant of a polyamine of the kind exemplified in the above Y having structure (a) and chlorinated trimellitic anhydride can be given. More specifically, the following General Formula (6) can be given.

[0047]

[0048] In General Formula (6), i, j, k, 1 are natural numbers, i + j = 6 to 17, and k + 1 = 8 to 19. The wavy line portion indicates a carbon-carbon single bond or a carbon-carbon double bond.

[0049] In the above General Formula (11), X 4 represents a 4- to 6-valent organic group, and Y represents a residue of a polycarboxylic acid component. As a polycarboxylic acid component, a tetracarboxylic acid, a tetracarboxylic dianhydride, or a tetracarboxylic diester dichloride can be given. X 4 represents a 2- to 6-valent organic group, and Y represents a polyamine residue. X 4 and Y 4at least any one of them represents an organic group containing one or more alicyclic structures and a plurality of hydrocarbon structures having 4 or more carbon atoms (hereinafter, sometimes abbreviated as "structure (b)"). That is, X 4 represents the case where the polybasic carboxylic acid residue has the structure (b), Y 4 represents the case where the polybasic amine residue has the structure (b), X 4 and Y 4 respectively represent the case where the polybasic carboxylic acid residue has the structure (b) and the case where the polybasic amine residue has the structure (b). By containing such a structure, the cured film obtained by curing the resin composition has high elongation, low dielectric constant, and low dielectric loss tangent.

[0050] With respect to the above structure (b), specific examples are described. As the alicyclic structure, any structure can be used, but a bicyclic ring or a tricyclic ring having a plurality of ring structures is preferable from the viewpoint of heat resistance. As specific examples of the alicyclic structure, in addition to the organic groups exemplified as specific examples of the alicyclic hydrocarbon of the above structure (a), a norbornyl group, a norbornenyl group, a tricyclodecanyl group, and the like can be given, and from the viewpoint of heat resistance, a norbornyl group, a norbornenyl group, and a tricyclodecanyl group are preferable.

[0051] As the hydrocarbon structure having 4 or more carbon atoms, in addition to the organic groups exemplified as specific examples of the hydrocarbon group having 4 to 12 carbon atoms which can have an unsaturated bond in the above structure (a), a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group can be given.

[0052] The above X having the structure (b) 4 is a polybasic amine residue, and as the polybasic amine compound, in addition to the polybasic amines exemplified in the above structure (a), a polybasic amine represented by the following general formula (12) can be given.

[0053]

[0054] In the general formula (12), u and t each represent an integer of 4 to 16.

[0055] The above Y having the structure (b) 4 is a polybasic carboxylic acid residue, and as the polybasic carboxylic acid, in addition to the polybasic carboxylic acids exemplified in the above structure (a), a polybasic carboxylic acid represented by the following general formula (13) can be given.

[0056]

[0057] In the general formula (13), o and p each represent an integer of 4 to 16.

[0058] The above-mentioned (A) component is preferably a resin having a structural unit represented by the above-mentioned general formula (1) and a structural unit represented by the following general formula (7). Further, it is preferable to have a structural unit represented by the above-mentioned general formula (11) and a structural unit represented by the following general formula (7). By having these structural units, it is possible to impart heat resistance and organic solvent solubility while maintaining low dielectric constant and low dielectric loss tangent.

[0059]

[0060] In general formula (7), X 2 represents a 4- to 6-valent organic group, Y 2 represents a 2- to 6-valent organic group. At least X 2 is X 3 , or Y 2 is Y 3 . X 3 represents any one or more of a 2- to 6-valent organic group containing any one or more of a bisphenol A skeleton, a biphenyl skeleton and a hexafluoroisopropylidene skeleton, or a residue of an acid anhydride represented by the following general formula (8). Y 3 represents any one or more of a 2- to 6-valent organic group containing any one or more of a bisphenol A skeleton, a biphenyl skeleton and a hexafluoroisopropylidene skeleton, or a residue of a diamine represented by the following formula (9). A plurality of R 3 may be the same or different, and represents a 1-valent organic group having an ethylenic unsaturated bond or a hydrogen atom. Not all of R 3 are hydrogen atoms. r represents an integer of 2 to 4. A plurality of R 4 may be the same or different, and represents a carboxyl group, a hydroxyl group or a 1-valent organic group having an ethylenic unsaturated bond. s represents an integer of 0 to 4. * represents a bonding point.

[0061]

[0062] In general formula (8), a represents an integer of 6 to 20. * represents a bonding point.

[0063] H2N-Y 4 -NH2(9)

[0064]

[0065] In general formula (9), * represents a bonding point.

[0066] In general formula (7), X 2 and X 3 are derived from a residue of a carboxylic acid residue or a derivative thereof. In the case where X 2 is X 3 , X 3As the carboxylic acid compound which is an acid residue, for example, 3,3',4,4'-diphenyltetracarboxylic acid, 2,3,3',4'-diphenyltetracarboxylic acid, 2,2',3,3'-diphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 4,4'-(4,4'-isopropylidenediphenyloxy)bis(o-phthalic acid), 4,4'-(4,4'-isopropylidenediphenyloxycarbonyl)bis(o-phthalic acid), and the carboxylic anhydride shown in the above general formula (7), and derivatives thereof can be given. Among them, from the viewpoints of solubility in an organic solvent, transparency, and low dielectric constant, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 4,4'-(4,4'-isopropylidenediphenyloxy)bis(o-phthalic acid) are preferred.

[0067] In the general formula (7), Y 2 and Y 3 is a residue derived from an amine residue or a derivative thereof. In the case where Y 2 is Y 3 , as the amino compound in which Y 3 is an amine residue, for example, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxy)biphenyl, 4,4'-diamino-6,6'-bis(trifluoromethyl)-[1,1'-biphenyl]-3,3'-diol, bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, or the diamine compound shown in the above general formula (8), or derivatives thereof can be given. Among them, from the viewpoints of solubility in an organic solvent, transparency, and low dielectric constant, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and the like aromatic diamines, and 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, and 1,3-bis(aminomethyl)cyclohexane in the general formula (9) are preferred.

[0068] X 1 As long as the requirements of general formula (1) are satisfied, other acid residues than the polybasic carboxylic acid residue having structure (a) can also be used. Furthermore, X 2 As long as the requirements of general formula (7) are satisfied, other acid residues than X 3 can also be used.

[0069] Furthermore, X 4 As long as the requirements of general formula (11) are satisfied, other acid residues than the polybasic carboxylic acid residue having structure (b) can also be used.

[0070] As the carboxylic acid compound that becomes the other acid residue, aromatic tetracarboxylic acids such as 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)sulfide, bis(3,4-dicarboxyphenyl)ether, 1,3-bis(3,4-dicarboxyphenoxy)benzene, trimellitic acid (3,4-dicarboxyphenyl) ester, 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, aliphatic tetracarboxylic acids such as bicyclo[3.1.1.]hept-2-ene tetracarboxylic acid, bicyclo[2.2.2.]octane tetracarboxylic acid, or adamantane tetracarboxylic acid, or the like can be given.

[0071] These acids can be used directly or in the form of anhydride, acid chloride, or active ester. As the activated ester group, the following structures can be given, but are not limited thereto.

[0072]

[0073] In the formula, A and D represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, a nitro group. * represents a bonding point.

[0074] Furthermore, by using a tetracarboxylic acid containing a silicon atom such as dimethylsilanedi phthalic acid or 1,3-bis(phthalic acid)tetramethyldisiloxane, the adhesion to the substrate, the resistance to oxygen plasma, UV ozone treatment used for washing, and the like can be improved. These tetracarboxylic acids containing a silicon atom are preferably used in an amount of 1 to 30 mol% of the total acid component.

[0075] Y 1 As long as the requirements of general formula (1) are satisfied, other amine residues than the polybasic amine residue having structure (a) can also be used. Furthermore, Y 2As long as the requirements of general formula (7) are met, it can also be divided into Y. 3 Other amine residues besides those mentioned above.

[0076] In addition, Y 4 As long as the requirements of general formula (11) are met, it can also be any amine residue other than the polyamine residue with structure (a).

[0077] Examples of polyamine compounds that can become other amine residues include, for example, aromatic diamines such as, m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthylenediamine, 2,6-naphthylenediamine, 9,10-anthraphthalenediamine, 4,4'-diaminobenzoylaniline, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, and bis[4] [(4-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(3-amino-4-hydroxyphenyl) ether, 3,4'-diaminodiphenylmethane, bis(3-amino-4-hydroxyphenyl)methylene, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2 2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 2-(4-aminophenyl)-5-aminobenzo[ azole, 2-(3-aminophenyl)-5-aminobenzo[a] azole, 2-(4-aminophenyl)-6-aminobenzo[a] azole, 2-(3-aminophenyl)-6-aminobenzo[a] azole, 1,4-bis(5-amino-2-benzo[]] (Zyzolyl)benzene, 1,4-bis(6-amino-2-benzo[]) (Azolyl)benzene, 1,3-bis(5-amino-2-benzo[]) (Zyzolyl)benzene, 1,3-bis(6-amino-2-benzo[]) (Azoxy)benzene, 2,6-bis(4-aminophenyl)benzobis azole, 2,6-bis(3-aminophenyl)benzobis( ... azole, bis[(3-aminophenyl)-5-benzo[] [[azole], bis[(4-aminophenyl)-5-benzo] [[azole], bis[(3-aminophenyl)-6-benzo[]] [[azole], bis[(4-aminophenyl)-6-benzo[]] [Azolyl], N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, 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)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl Aromatic diamines such as (-3,3'-diamino-4,4-dihydroxybiphenyl), 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl ester of 4-aminobenzoic acid, and 1,3-bis(4-anilino)tetramethyldisiloxane, and compounds obtained by substituting a portion of the hydrogen atoms of these aromatic rings with alkyl, fluoroalkyl, or halogen atoms having 1 to 10 carbon atoms, etc., but not limited thereto.

[0078] The aforementioned polyamine compounds can be used directly or as compounds in which the amine site is isocyanated or trimethylsilylated. Furthermore, two or more of these polyamine compounds can be used in combination.

[0079] Examples of aliphatic diamines include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Examples of diamines having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane. These are preferred because they can improve adhesion to the substrate.

[0080] The multiple R in the above general formula (1) 1 Multiple R in general formula (7) 3 and multiple R in general formula (11) 8at least one is a monovalent organic group having an ethylenically unsaturated bond. As a method for introducing the organic group having an ethylenically unsaturated bond, for example, a method in which a tetracarboxylic dianhydride is reacted with an alcohol having an ethylenically unsaturated bond to form a tetracarboxylic diester, and then the amide polycondensation is performed with a polyamine compound is exemplified. As other methods, a method in which trifluoroacetic acid and an alcohol having an ethylenically unsaturated bond are reacted with a polyamic acid obtained from an acid dianhydride and a diamine, and the like are exemplified.

[0081] As the method for producing the above-described tetracarboxylic diester, the above-described acid dianhydride and alcohol can be directly reacted in a solvent, but from the viewpoint of reactivity, it is preferable to use a reaction activator. As the reaction activator, tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine, and 1,8-diazabicycloundecene are exemplified. As the addition amount of the reaction activator, it is preferable that the reaction activator is 3 mol% or more and 300 mol% or less, and more preferably 20 mol% or more and 150 mol% or less, with respect to the acid anhydride group that is subjected to the reaction. In addition, a small amount of a polymerization inhibitor can be used for the purpose of preventing the crosslinking at the ethylenically unsaturated bond site in the reaction. Thereby, in the reaction of the alcohol having an ethylenically unsaturated bond, which has low reactivity, and the tetracarboxylic dianhydride, the reaction can be promoted by heating in the range of 120°C or lower. As the polymerization inhibitor, phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene are exemplified. 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 alcohol.

[0082] As the above-described amide polycondensation reaction, various methods are exemplified. A method in which the tetracarboxylic diester is subjected to acid chloride treatment and then reacted with a diamine, a method using a carbodiimide-based dehydration condensing agent, and a method in which activated esterification is performed and then reacted with a diamine are exemplified. Among them, the method in which activated ester is an intermediate is preferable because the reactivity is good regardless of the selection of either aromatic diamine or aliphatic diamine as a monomer.

[0083] As the alcohol having an ethylenic unsaturated bond described above, (meth)acrylate having a hydroxyl group or unsaturated fatty acid-modified alcohol can be given. As the (meth)acrylate having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2-propyl alcohol, 2-(meth)acrylamidoethyl alcohol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-t-butoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexylalkoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol-1,3-di(meth)acrylate, glycerol-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol-1-allyloxy-3-methacrylate, glycerol-1-allyloxy-2-methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1,3-diyl bis(2-methacrylate), 2-(acryloyloxy)-2-(hydroxymethyl)butyl methacrylate, and the like having two or more ethylenic unsaturated bonds and one hydroxyl group, and the like can be given. Here, the term "(meth)acrylate" means methacrylate or acrylate. The same applies to similar expressions.

[0084] As the unsaturated fatty acid-modified alcohol, unsaturated fatty acid-modified alcohol having 6 or more carbon atoms can be given. From the viewpoint of exposure sensitivity, alcohol having an unsaturated group at the terminal or a double bond having a cis structure is preferred, and from the viewpoint of dielectric constant and dielectric loss tangent, alcohol having 12 or more carbon atoms is preferred. As specific examples of the unsaturated fatty acid-modified alcohol, 5-hexen-1-ol, 3-hexen-1-ol, 6-hepten-1-ol, cis-5-octen-1-ol, cis-3-octen-1-ol, cis-3-nonen-1-ol, cis-6-nonen-1-ol, 9-decan-1-ol, cis-4-decan-1-ol, 10-undecen-1-ol, 11-dodecan-1-ol, elaidolinoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and erucyl alcohol, and the like can be given. Among them, from the viewpoint of dielectric properties and exposure sensitivity of the obtained cured film, oleyl alcohol, linoleyl alcohol, and linolenyl alcohol are preferred.

[0085] In the reaction of the anhydride with the alcohol having an ethylenic unsaturated bond, other alcohols can also be used at the same time. The other alcohols can be appropriately selected depending on adjustment of the exposure sensitivity, adjustment of the solubility in the organic solvent, and the like for various purposes. Specifically, aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isopentyl alcohol, or monomethyl ether of ethylene glycol, monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monomethyl ether of diethylene glycol, monoethyl ether of diethylene glycol, monobutyl ether of diethylene glycol, monomethyl ether of triethylene glycol, monoethyl ether of triethylene glycol, monobutyl ether of triethylene glycol, monomethyl ether of propylene glycol, monoethyl ether of propylene glycol, monobutyl ether of propylene glycol, monomethyl ether of dipropylene glycol, monoethyl ether of dipropylene glycol, monobutyl ether of dipropylene glycol, monomethyl ether of tripropylene glycol, monoethyl ether of tripropylene glycol, monobutyl ether of tripropylene glycol, and the like derived from alkylene oxide can be mentioned.

[0086] As R 1 in the general formula (1), R 3 in the general formula (7), and the plurality of R 8 in the general formula (11), a method of introducing an organic group having an ethylenic unsaturated bond can be via an ionic bond. As a method of introducing an organic group having an ethylenic unsaturated bond by using an ionic bond, a method in which a polyamic acid obtained by the reaction of an acid dianhydride and a diamine is reacted with a tertiary amine having an ethylenic unsaturated bond can be mentioned. As the tertiary amine having an ethylenic unsaturated bond, a compound represented by the following general formula (10) can be mentioned.

[0087]

[0088] In the general formula (10), R 5 represents a hydrogen atom or a methyl group. R 6 and R 7 each independently represent any one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and a phenyl group. b represents an integer of 1 to 10.

[0089] Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylaminopropyl (meth)acrylate are preferable in that they easily improve the exposure sensitivity.

[0090] Further, in order to improve the storage stability of the photosensitive resin composition of the present application, to exhibit various functions, the end of the main chain of the (A) component can be capped with a capping agent. As the capping agent, monamines, acid anhydrides, monocarboxylic acids, monochloroformic compounds, monoactive ester compounds, and the like can be given. Further, a monohydric alcohol can be used as the capping agent in the later stage of the reaction of the above-mentioned amide polycondensation. Further, by capping the end of the resin with a capping agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the exposure sensitivity, the mechanical properties of the obtained cured film, and the like can be easily adjusted to a preferable range.

[0091] The ratio of the introduction of the capping agent is preferably 0.1 mol% or more and 60 mol% or less, and particularly preferably 5 mol% or more and 50 mol% or less, from the viewpoints of the solubility in a developing solution and the mechanical properties of the obtained cured film. A plurality of capping agents can be reacted to introduce a plurality of different end groups.

[0092] As the monamine used as the capping agent, known compounds can be used, but aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 1-hydroxy-7-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 3-aminobenzoic acid, 3-aminophenol, 3-aminophenylthiol, and the like are preferable. Two or more of them can be used.

[0093] As the acid anhydride, monocarboxylic acid, monochloroformic compound, monoactive ester compound, known compounds can be used, but phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, and the like can be given as the acid anhydride, itaconic anhydride, and the like. Two or more of them can be used.

[0094] As the monohydric alcohol used as the capping agent, the same substances as exemplified as the alcohol reacting with the above-mentioned acid anhydride can be given.

[0095] Further, the monomer containing structure (a) and the capping agent introduced into the (A) component used in the present application can be easily detected by the following method. For example, by dissolving the resin into which the capping agent is introduced in an acidic solution, decomposing into the amine component and the acid anhydride component as the structural unit, and subjecting to gas chromatography (GC), NMR measurement, the capping agent used in the present application can be easily detected. Further, for the GC measurement, by simultaneously measuring the external standard substance in which the peak does not overlap with each component, comparing the integral value of each peak of the chromatogram with the external standard substance, the molar ratio of each monomer including the capping agent can be estimated. In addition thereto, by directly subjecting to pyrolysis gas chromatography (PGC), infrared spectroscopy, H-NMR spectroscopy, and the like of the resin component into which the capping agent is introduced, the capping agent used in the present application can be easily detected. 1 H-NMR spectroscopy, 13C-NMR spectrum and 2-dimensional NMR spectrum are measured, and can be easily detected. In this case, the molar ratio of each monomer can be determined from the integral value of the infrared spectrum, 1 The molar ratio of each monomer is analyzed from the integral value of the H-NMR spectrum or 2-dimensional NMR.

[0096] The (A) component in the present application preferably has a weight average molecular weight of 5,000 or more and 100,000 or less. The weight average molecular weight is converted to polystyrene by GPC (gel permeation chromatography) and is 5,000 or more, so that the mechanical properties such as elongation, breaking strength, and elastic modulus after curing can be improved. On the other hand, by making the weight average molecular weight 100,000 or less, the developability can be improved. In order to obtain the mechanical properties, it is more preferable to be 20,000 or more. Further, in the case where the (A) component contains two or more kinds of resins, it is only necessary that the weight average molecular weight of at least one kind is in the above range.

[0097] Further, the (A) component used in the present application is preferably polymerized using a solvent. As to the polymerization solvent, it is only necessary that the acid component, the amine component, the alcohol, and the catalyst as the raw material monomers can be dissolved, and the kind is not particularly limited. For example, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-hexalactone, ε-hexalactone, α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate, propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol, p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like can be mentioned.

[0098] The photosensitive resin composition of the present application contains a (B) photopolymerization initiator. By containing the (B) photopolymerization initiator, it is possible to perform the patterning through the exposure and development processes. The (B) photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical by exposure, but alkylphenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, oxime ester compounds, and benzoic acid ester compounds are preferable because of their excellent sensitivity, stability, and ease of synthesis. Among them, alkylphenone compounds and oxime ester compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are particularly preferable. Further, in the case of processing a thick film having a film thickness of 5 μm or more, phosphine oxide compounds are preferable from the viewpoint of resolution.

[0099] As the alkylphenone compound, for example, 2-methyl-[4-(methylthio)phenyl]-2- morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- phenyl)-butan-1-one, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the like α-aminoalkylphenone compound, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4- isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2- hydroxy-2-propyl)ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl-phenyl ketone, benzoin, and the like α-hydroxyalkylphenone compound, 4-benzoyl-4-methylphenyl ketone, 2,3- diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2- methylpropiophenone, p-tert-butyldichloroacetophenone, benzyl methoxyethyl acetal, 2,3- diethoxyacetophenone, benzil dimethyl ketal, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like α-alkoxyalkylphenone compound, acetophenone, p-tert- butyldichloroacetophenone, and the like acetophenone compound. Among them, 2-methyl-[4- (methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- morpholin-4-yl-phenyl)-butan-1-one, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- butanone-1 and the like α-aminoalkylphenone compound are preferable because of high sensitivity.

[0100] As the phosphine oxide compound, for example, 6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4- trimethylpentyl)-phosphine oxide.

[0101] As the oxime ester compound, for example, 1-phenyl-1,2-propanedione-2-(o- ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1- phenyl-2-(benzoyloximino)-1-propanone, 2-octanedione, 1-[4-(phenylthio)-2-(O- benzoyloxime)], 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1,3- diphenylpropane trione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-phenyl-1,2- propanedione-2-(o-benzoyl)oxime, 1-phenyl-3-ethoxypropane trione-2-(o- benzoyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), NCI- 831, NCI-930 (all, manufactured by ADEKA), OXE-03, OXE-04 (all, manufactured by BASF), and the like can be given. Among them, from the viewpoint of sensitivity, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), 2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], NCI-831, NCI-930, OXE-03, OXE-04 are preferable.

[0102] As the aminobenzophenone compound, for example, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone can be given.

[0103] As the diketone compound, benzil can be given.

[0104] As the ketone ester compound, methyl benzoylformate, ethyl benzoylformate can be given.

[0105] As the benzoic acid ester compound, o-benzoylbenzoic acid methyl ester, ethyl p- dimethylaminobenzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, ethyl p- diethylaminobenzoate can be given.

[0106] As other specific examples of the above-mentioned (B) photopolymerization initiator, mention can be made of benzophenone, 4-benzoyl-4'-methylbenzophenone, dibenzyl ketone, fluorenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(l-oxo-2-propenyl oxy)ethyl]benzylammonium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-l-propenium chloride monohydrate, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-l- propenium chloride, anthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzoanthrone, dibenzo-cycloheptanone, methyleneanthrone, 4-azidobenzylideneacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, carbon tetra-bromide, tribromophenyl sulfone, and the like.

[0107] As the content of the (B) photopolymerization initiator, it is preferable that it be 0.5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total of the (A) component and the (D) compound having two or more ethylenic unsaturated bonds described later, as necessary, in order to obtain sufficient sensitivity and to suppress the amount of outgassing at the time of thermal curing. More preferably, it is 1.0 parts by mass or more and 10 parts by mass or less.

[0108] The photosensitive resin composition of the present application can contain a sensitizer for the purpose of improving the function of the (B) photopolymerization initiator. By containing a sensitizer, it is possible to improve sensitivity and adjust the photosensitive wavelength. As the sensitizer, mention can be made of bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine, and derivatives thereof, and the like, but it is not limited thereto.

[0109] The photosensitive resin composition of the present application preferably further contains (C) a compound having 2 or more ethylenic unsaturated bonds (hereinafter, sometimes abbreviated as "(C) component"). The molecular weight of the (C) component is preferably 100 or more and 2000 or less. By containing the (C) component, the crosslinking density at the time of exposure is increased and thus the exposure sensitivity is further improved, which is helpful for the reduction of the exposure amount and the film reduction amount.

[0110] As the (C) component, a publicly known (meth)acrylate compound can be contained, and a multifunctional (meth)acrylate containing an alicyclic structure is particularly preferable because it can have a low dielectric constant, a low dielectric loss tangent and an exposure sensitivity at a high level.

[0111] As the multifunctional (meth)acrylate containing an alicyclic structure, for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, 1,3-adamantanol di(meth)acrylate, 1,3,5-adamantantriol di(meth)acrylate, 1,3,5-adamantantriol tri(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, (2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene or 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene can be mentioned. Among them, dimethylol-tricyclodecane di(meth)acrylate, 1,3-adamantanol di(meth)acrylate, 1,3,5-adamantantriol di(meth)acrylate, 1,3,5-adamantantriol tri(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate and the like can be mentioned.

[0112] As the compound of the other (C) component, for example, an epoxy (meth) acrylate obtained by reacting a polyfunctional epoxy compound with a (meth) acrylic acid can be given. The epoxy (meth) acrylate can be used for the purpose of improving the alkali developability because of the addition of hydrophilicity. As the polyfunctional epoxy compound, for example, the following compounds can be given. These polyfunctional epoxy compounds are preferred because of excellent heat resistance and chemical resistance.

[0113]

[0114] As the content of the (C) component, 5 parts by mass or more and 100 parts by mass or less, preferably 10 parts by mass or more and 40 parts by mass or less, with respect to 100 parts by mass of the (A) component is preferred. In the case of being in such a range, it is easy to obtain the effect of improving the exposure sensitivity and the low dielectric constant and low dielectric tangent.

[0115] The photosensitive resin composition of the present application can contain an antioxidant. By containing the antioxidant, yellowing of the cured film and the decrease in mechanical properties such as elongation at the time of the heat treatment of the subsequent process are suppressed. Further, by the rust-preventing effect on the metal material, oxidation of the metal material can be suppressed, and thus it is preferred.

[0116] As the antioxidant, a hindered phenol-based antioxidant or a hindered amine-based antioxidant is preferred.

[0117] As the hindered phenol-based antioxidant, for example, Irganox 245, Irganox 3114, Irganox 1010, Irganox 1098, Irganox 1135, Irganox 259, Irganox 1035 (all, trade names, manufactured by BASF Corporation), or 2,6-di(tert-butyl)-p-cresol can be given, but not limited thereto.

[0118] As the hindered amine-based antioxidant, for example, TINUVIN 144, TINUVIN 292, TINUVIN 765, TINUVIN 123 (all, trade names, manufactured by BASF Corporation), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, or tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetra carboxylate can be given.

[0119] As other antioxidants, phenol, catechol, resorcinol, hydroquinone, 4-tert-butylcatechol, 2,6-di(tert-butyl)-p-cresol, phenothiazine, 4-methoxyphenol can be given. As the addition amount of the antioxidant, 0.1 parts by mass or more and 10.0 parts by mass or less, relative to 100 parts by mass of the (A) component, is preferable, and 0.3 parts by mass or more and 5.0 parts by mass or less is more preferable. In the case of being in such a range, the developability and the discoloration inhibition effect due to heat treatment can be moderately maintained.

[0120] The photosensitive resin composition of the present application can have a heterocyclic compound containing a nitrogen atom. By having a heterocyclic compound containing a nitrogen atom, high adhesion to a substrate of a metal that is easily oxidized such as copper, aluminum, silver, and the like can be obtained. The mechanism is not clear, but it is presumed that this is because of the interaction with the metal surface by the metal coordination ability of the nitrogen atom, and the stabilization of the interaction by the bulkiness of the heterocyclic ring.

[0121] As the heterocyclic compound containing a nitrogen atom, imidazole, pyrazole, indazole, carbazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof can be given.

[0122] As the heterocyclic compound containing a nitrogen atom, from the viewpoint of reactivity with metals and the like, 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, and the like are preferable.

[0123] As the addition amount of the heterocyclic compound containing a nitrogen atom, 0.01 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the (A) component, is preferable, and 0.05 parts by mass or more and 3.0 parts by mass or less is more preferable. In the case of being in such a range, the developability and the stabilization effect of the substrate metal can be moderately maintained.

[0124] The photosensitive resin composition of the present application can contain a solvent. As the solvent, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, and the like, water, and the like can be given. alkyl ethers such as methyl ether, ethyl ether, propyl ether, butyl ether, and the like, acetone, methyl ethyl ketone, diisobutyl ketone, and the like, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and the like, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, and the like, toluene, xylene, and the like, and the like. Two or more of them can be contained.

[0125] The content of the solvent is preferably 100 parts by mass or more for the purpose of dissolving the composition, and is preferably 1,500 parts by mass or less for the purpose of forming a coated film having a film thickness of 1 μm or more, with respect to 100 parts by mass of the (A) component.

[0126] The photosensitive resin composition of the present application can contain, as needed, a surfactant, ethyl lactate, propylene glycol monomethyl ether acetate, and the like, esters, ethanol, and the like, ketones such as cyclohexanone, methyl isobutyl ketone, and the like, tetrahydrofuran, dioxolane, and the like, ethers such as diethyl ether, and the like, and the like, for the purpose of improving the wettability with respect to a substrate. alkyl ethers such as methyl ether, ethyl ether, propyl ether, butyl ether, and the like, acetone, methyl ethyl ketone, diisobutyl ketone, and the like, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and the like, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, and the like, toluene, xylene, and the like, and the like. Two or more of them can be contained.

[0127] Further, for the purpose of improving the adhesion with respect to a substrate, a silane coupling agent can be contained as a silicon component in the photosensitive resin composition of the present application, within a range that does not impair the storage stability. As the silane coupling agent, there can be mentioned trimethoxysilylaminopropylsilane, trimethoxysilylcyclohexyloxyethylsilane, trimethoxysilylvinylsilane, trimethoxysilylthiolpropylsilane, trimethoxysilylglycidyloxypropylsilane, tris(trimethoxysilylpropyl)isocyanurate, triethoxysilylaminopropylsilane, triethoxysilylcyclohexyloxyethylsilane, triethoxysilylvinylsilane, triethoxysilylthiolpropylsilane, triethoxysilylglycidyloxypropylsilane, tris(triethoxysilylpropyl)isocyanurate, and a reaction product of trimethoxysilylaminopropylsilane or triethoxysilylaminopropylsilane with an anhydride. The reaction product can be used in a state of an amide acid or in a state in which imidization has been performed. As the anhydride that is reacted, there can be mentioned succinic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, and 4,4'-oxydiphthalic anhydride. The preferred content of the silane coupling agent is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) component.

[0128] Next, the shape of the photosensitive resin composition of the present application will be described.

[0129] The photosensitive resin composition of the present application is not limited in shape as long as it contains the above-mentioned (A) component and (B) photopolymerization initiator, and can be, for example, paste-shaped or sheet-shaped.

[0130] Further, the so-called photosensitive sheet of the present application refers to a sheet-like substance in a state of being not completely cured, which is obtained by coating the photosensitive resin composition of the present application on a support, and drying at a temperature and time range in which the solvent can be volatilized, and which is soluble in an organic solvent or an aqueous alkali solution.

[0131] The support is not particularly limited, and various films generally commercially available such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, a polyimide film, etc. can be used. In order to improve adhesion and peeling properties, a surface treatment with a silicone, a silane coupling agent, an aluminum chelating agent, a polyurea, etc. can be applied to the interface of the support and the photosensitive resin composition. Further, the thickness of the support is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 μm. Further, in order to protect the film surface of the photosensitive composition obtained by coating, a protective film can also be provided on the film surface. Thereby, the surface of the photosensitive resin composition can be protected from contaminating substances such as garbage, dirt, etc. in the atmosphere.

[0132] As a method of coating the photosensitive resin composition on the support, spin coating using a spin coater, spray coating, roll coating, screen printing, knife coater, die coater, calender coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. can be mentioned. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but generally, the film thickness after drying is preferably 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity, etc.

[0133] Drying can be performed using an oven, an electric hot plate, infrared rays, etc. The drying temperature and the drying time are only required to be in a range in which the solvent can be volatilized, and it is preferable to appropriately set the range in which the photosensitive resin composition becomes an uncured or semi-cured state. Specifically, it is preferable to perform heating in the range of 40°C to 150°C for 1 minute to several tens of minutes. Further, these temperatures can be combined and the temperature can be increased in stages, for example, each of 80°C and 90°C can be heat-treated for 2 minutes.

[0134] Next, a method of forming a relief pattern of a cured film using the photosensitive resin composition or the photosensitive sheet of the present application will be described.

[0135] The photosensitive resin composition of the present application is coated on a substrate, or the above-mentioned photosensitive sheet is laminated on a substrate. As the substrate, a plated copper substrate, a silicon wafer can be used, and as the material, ceramics, gallium arsenide, etc. can be used, but is not limited thereto. As the coating method, spin coating using a spin coater, spray coating, roll coating, etc. can be used. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., and generally, the coating is performed in such a manner that the film thickness after drying becomes 0.1 to 150 μm.

[0136] In order to improve the adhesion of the substrate to the photosensitive resin composition, the substrate can also be pretreated with the above-mentioned silane coupling agent. For example, a solution in which the silane coupling agent is dissolved at 0.5 to 20 mass% in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. is prepared. Next, the prepared solution is used to perform surface treatment on the substrate by spin coating, immersion, spray coating, vapor treatment, etc. Depending on the case, heat treatment at 50°C to 300°C is then performed to allow the reaction of the substrate with the silane coupling agent to proceed.

[0137] Next, the substrate on which the photosensitive resin composition is coated, or the photosensitive sheet of the present application is laminated is dried to obtain a photosensitive resin composition film. The drying is preferably performed using an oven, an electric hot plate, infrared rays, etc. in the range of 50°C to 150°C for 1 minute to several hours. Note that in the case of the photosensitive sheet, the drying step can not necessarily be performed.

[0138] Next, the photosensitive resin composition film is exposed by irradiating chemical rays through a mask having a desired pattern. As the chemical rays used for the exposure, ultraviolet rays, visible rays, electron rays, X-rays, etc. can be used, but in the present application, i-rays (365 nm), h-rays (405 nm), g-rays (436 nm) of a mercury lamp are preferably used.

[0139] Next, the exposed photosensitive resin composition film can be subjected to a post-exposure baking (PEB) step as necessary. The PEB step is preferably performed using an oven, an electric hot plate, infrared rays, etc. in the range of 50°C to 150°C for 1 minute to several hours.

[0140] Next, the exposed photosensitive resin film is subjected to development. In forming a pattern of the resin, after exposure, the unexposed portion is removed using a developing solution. As the developing solution used for development, a good solvent with respect to the photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferable. As the good solvent, for example, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like are preferable. As the poor solvent, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, and the like are preferable. In the case of using a mixture of the good solvent and the poor solvent, the proportion of the poor solvent with respect to the good solvent is preferably adjusted according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more kinds of solvents, for example, a plurality of kinds can be combined and used.

[0141] In addition, in the case where the photosensitive resin composition is dissolved in an aqueous alkali solution, development with an aqueous alkali solution can be performed. The developing solution used for development is a substance that dissolves and removes the alkali-soluble polymer, and is typically an aqueous alkali solution in which an alkali compound is dissolved. As the alkali compound, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, 1,6-hexanediamine, and the like can be given. In addition, depending on the case, these aqueous alkali solutions can also contain one or a combination of a plurality of kinds of polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, and the like.

[0142] After development, rinsing treatment with an organic solvent or water is preferably performed. In the case of using an organic solvent, in addition to the developing solution described above, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like can be given. In the case of using water, alcohols such as ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and the like can be added to the water and used for rinsing treatment.

[0143] Next, the photosensitive resin film after development is subjected to heat treatment. After development, heat cross-linking reaction is performed by applying a temperature of 150°C to 400°C to cure it. The heat treatment is performed at a certain temperature, in stages with temperature increase, or in a certain temperature range while continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. As the lower limit of the curing conditions in the present application, it is preferable to be 170°C or higher, but it is more preferable to be 180°C or higher in order to sufficiently perform the curing. Further, there is no particular limitation on the upper limit of the curing conditions, but it is preferable to be 280°C or lower, more preferable to be 250°C or lower, and further preferable to be 230°C or lower from the viewpoint of film shrinkage and stress suppression. Further, as the lower limit, it is preferable to be 250°C or higher and as the upper limit, it is preferable to be 350°C or lower for the purpose of increasing the glass transition temperature or the thermal decomposition temperature.

[0144] The cured film formed by the photosensitive resin composition of the present application can be used as an insulating film or a protective film constituting an electronic component.

[0145] Here, as the electronic component, active components having a semiconductor such as transistors, diodes, integrated circuits (ICs), memories, and passive components such as resistors, capacitors, inductors, and antenna elements can be given. Further, the electronic component using a semiconductor is also referred to as a semiconductor device.

[0146] As a specific example of the cured film in the electronic component, a passivation film for a semiconductor, a surface protective film for a semiconductor element, a TFT (Thin Film Transistor), an interlayer insulating film such as an interlayer insulating film between rewiring lines in a multilayer wiring of 2 to 10 layers for high-density mounting, an insulating film for a touch panel display, a protective film, an insulating layer for an organic electroluminescent element, and the like are suitable, but are not limited thereto, and various structures can be employed.

[0147] Further, the substrate surface on which the cured film is formed can be appropriately selected depending on the purpose and the process, and silicon, ceramics, glass, metal, epoxy resin, and the like can be given, and a plurality of them can be arranged in the same surface.

[0148] Next, an application example to a semiconductor device having a bump using a cured film obtained by curing the photosensitive resin composition of the present application will be described using the drawings. Figure 1 An enlarged cross-sectional view of a pad portion of the semiconductor device having a bump of the present application. As shown in FIG. 1, a semiconductor device 1 having a bump is provided with a substrate 2, a semiconductor element 3, a bump 4, and a protective film 5. Figure 1As shown, for silicon wafer 1, a passivation film 3 is formed on aluminum (hereinafter abbreviated as Al) pads 2 for input / output, and this passivation film 3 has through holes. An insulating film 4 is formed thereon as a pattern formed by curing the photosensitive resin composition of the present invention. Further, a metal (Cr, Ti, etc.) film 5 is formed in a manner connected to the Al pads 2, and metal wiring (Al, Cu, etc.) 6 is formed by electroplating or the like. Regarding the metal film 5, the periphery of the solder bumps 10 is etched to insulate the pads. A barrier metal 8 and solder bumps 10 are formed in the insulated pads. The curing film obtained by curing the photosensitive resin composition of the insulating film 7 can be thick-film processed in the scribe line 9.

[0149] Next, the detailed manufacturing method of semiconductor devices will be recorded in [the following text]. Figure 2 In the middle. For example Figure 2 As shown in 2a, input / output Al pads 2 and a further passivation film 3 are formed on the silicon wafer 1, and an insulating film 4 is formed as a pattern formed by curing a cured film obtained by curing the photosensitive resin composition of the present invention. Next, as... Figure 2 As shown in 2b, the metal (Cr, Ti, etc.) film 5 is formed in a manner that connects to the Al pad 2, as shown in 2b. Figure 2 As shown in 2c, the film metal wiring 6 is formed by a deposition method. Next, as... Figure 2 As shown in 2d', the photosensitive resin composition of the present invention before curing is coated, and after a photolithography process, it serves as... Figure 2 An insulating film 7 is formed by creating a pattern as shown in 2d. At this time, the photosensitive resin composition of the insulating film 7 before curing undergoes thick-film processing in the cutting groove 9. In the case of forming a multilayer wiring structure with three or more layers, the above process can be repeated to form each layer.

[0150] Next, as Figure 2 As shown in 2e and 2f, barrier metal 8 and solder bumps 10 are formed. Then, the chip is divided into individual chips by cutting along the final dicing path 9. If the insulating film 7 is not patterned in the dicing path 9 or if residue remains, cracks may occur during cutting, affecting the reliability evaluation of the chip. Therefore, the excellent patterning process provided by the present invention for thick film processing is highly preferred for achieving high reliability of semiconductor devices.

[0151] Next, an antenna element using a cured film obtained by curing the photosensitive resin composition of the present invention will be described. Figure 3This is a schematic diagram of a coplanar-fed microstrip antenna, a type of planar antenna. 3a shows a cross-sectional view, and 3b shows a top view. First, the formation method will be described. The photosensitive resin composition of the present invention is coated onto a copper foil and pre-baked. After exposure, the copper foil is laminated and thermally cured to form a cured film with copper foil on both sides. Then, a pattern is formed using a subtractive method to obtain a microstrip antenna with... Figure 3 The antenna element is an antenna with a copper wiring pattern of microstrip line (MSL).

[0152] Next, for Figure 3 The antenna pattern is explained below. In 3a, 35 represents the ground plane (the entire surface), and 36 represents the insulating film that forms the substrate of the antenna. The upper layers 31 to 33 represent the cross-sections of the antenna wiring obtained by forming the above pattern. The ground wiring thickness J and the antenna wiring thickness K are arbitrary thicknesses depending on the impedance design, but are generally 2 to 20 μm. In 3b, 31 represents the antenna section, 32 represents the matching circuit, 33 represents the MSL feed line, and 34 represents the feed point. To achieve impedance integration between the antenna section 31 and the feed line 33, the length M of the matching circuit 32 has a length of 1 / 4λr (λr = (wavelength of the transmitted radio wave) / (dielectric constant of the insulating material)). 1 / 2 Furthermore, the width W and length L of the antenna section 31 are designed to be 1 / 2λr. The length L of the antenna section can also 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 a high-efficiency, high-profit antenna element. Furthermore, based on these characteristics, the antenna element using the insulating film of the present invention is suitable as a high-frequency antenna, by making the area of ​​the antenna section (=L×W) 1000mm². 2 The following dimensions allow for the formation of small antenna elements. This operation results in highly efficient, profitable, and compact antenna elements designed for high frequencies.

[0153] Next, a semiconductor package comprising an IC chip (semiconductor element), a redistribution layer, sealing resin, and antenna wiring will be described. Figure 4A cross-sectional view of a semiconductor package including an IC chip (semiconductor element), redistribution layer, sealing resin, and antenna element is shown. On an electrode pad 402 of an IC chip 401, a redistribution layer (copper 2 layer, insulating film 3 layer) including a copper wiring 409 and an insulating film 410 formed of the cured film of the present application is formed. On the pad of the redistribution layer (copper wiring 409 and insulating film 410), a barrier metal 411 and a solder bump 412 are formed. In order to seal the above-mentioned IC chip, a first sealing resin 408 using the cured film of the present application is formed, and further, a copper wiring 409 serving as a ground for an antenna is formed thereon. A first via wiring 407 connecting the ground 406 and the redistribution layer (copper wiring 409 and insulating film 410) is formed via a via formed in the first sealing resin 408. On the first sealing resin 408 and the ground wiring 406, a second sealing resin 405 using the cured film of the present application is formed, and a planar antenna wiring 404 is formed thereon. A second via wiring 403 connecting the planar antenna wiring 404 and the redistribution layer (copper wiring 409 and insulating film 410) is formed via a via formed in the first sealing resin 408 and the second sealing resin 405. The thickness of each layer of the insulating film 410 is preferably 10 to 20 μm, and the thickness of the first sealing resin and the second sealing resin is preferably 50 to 200 μm and 100 to 400 μm, respectively. The cured film of the present application has a low dielectric constant and a low dielectric loss tangent, and thus the resulting semiconductor package including an antenna element is highly efficient and profitable, and has a small transmission loss in the package.

[0154] That is, the electronic component of the present application is preferably: an electronic component including at least an antenna element including one or more antenna wirings and the cured film of the present application, and each of the antenna wirings includes one or more selected from a meander-shaped loop antenna, a coil-shaped loop antenna, a meander-shaped monopole antenna, a meander-shaped dipole antenna, and a planar antenna, and the area of each antenna portion of the antenna wiring is 1000 mm 2 Hereinafter, the cured film is an insulating film for insulating a ground from an antenna wiring.

[0155] Further, the electronic component of the present application is preferably: an electronic component including at least a semiconductor package including a semiconductor element, a redistribution layer, a sealing resin, and an antenna wiring, the insulating layer of the redistribution layer and / or the sealing resin includes the cured film of the present application, and the sealing resin also functions as an insulating film for insulating a ground from an antenna wiring.

[0156] Example

[0157] The following describes the present application using examples, but the present application is not limited by these examples. First, the evaluation method in each example and comparative example is described. In the evaluation, a photosensitive resin composition before curing (hereinafter referred to as varnish) filtered in advance with a filter made of polytetrafluoroethylene having an average pore diameter of 1 μm (manufactured by Sumitomo Electric Industries, Ltd.) was used.

[0158] (1) Molecular weight measurement

[0159] (A) The weight average molecular weight (Mw) of the components was confirmed using a GPC (gel permeation chromatography) device Waters 2690-996 (manufactured by Japan Waters Co., Ltd.). The measurement was performed with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent, and the weight average molecular weight (Mw) and the dispersity (PDI = Mw / Mn) were calculated in terms of polystyrene.

[0160] (2) Pattern processing property

[0161] (2)-1 Development property and sensitivity

[0162] After the varnish was spin-coated on a silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), a pre-baking film having a film thickness of 11 μm was produced by pre-baking at 120°C for 3 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Manufacturing Co., Ltd.). The obtained pre-baking film was exposed to light using a parallel light mask exposure machine (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) with an ultrahigh pressure mercury lamp as the light source (g, h, i ray mixture) via a gray scale mask for sensitivity measurement (a pattern having 1 : 1 line & gap 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, 40 μm and 50 μm. Regions having transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50% and 60% respectively.) by contact at 1000 mJ / cm 2 exposure. Then, after exposure post-baking at 120°C for 3 minutes, development was performed using a coating development device MARK-7. 2-minute spray development was performed using cyclopentanone (CP), followed by rinsing for 30 seconds with propylene glycol monomethyl ether acetate (PGMEA). In the case of over- or under-development, the development time and the rinsing time were appropriately adjusted.

[0163] The film thickness after development was measured, and the minimum exposure amount at which the film thickness of the 1000 mJ exposed portion was more than 95 times the film thickness when the film thickness was 100 was set as the optimum exposure amount. In addition, the residual film rate of the film thickness at the optimum exposure amount divided by the prebake film thickness was measured. Cases where the residual film rate was 90% or more were set as sensitivity A, cases where the residual film rate was 80% or more and less than 90% were set as B, cases where the residual film rate was 70% or more and less than 80% were set as C, cases where the residual film rate was 50% or more and less than 70% were set as D, and cases where the residual film rate was less than 50% were set as E, and the sensitivity was evaluated. In addition, the exposure amount was measured using an I-ray illuminometer. Note that the film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Manufacturing Co., Ltd. with a refractive index of 1.629. The film thicknesses described below were also measured in the same manner.

[0164] (2) Resolution

[0165] The minimum pattern size after development at the optimum exposure amount defined in (2)-1 was measured.

[0166] (3) Measurement of dielectric constant and dielectric tangent

[0167] After the varnish was applied on a 6-inch silicon wafer by the spin coating method using a coating and developing device ACT-8 so that the film thickness after prebaking at 120°C for 3 minutes became 11 μm and was prebaked, 300 mJ / cm2 2 exposure was performed using a PLA, and heating treatment was performed at each temperature for 1 hour using an inert oven CLH-21CD-S manufactured by Sanyo Thermo System Co., Ltd. at a temperature increase rate of 3.5°C / min to 320°C at an oxygen concentration of 20 ppm or less. The silicon wafer was taken out when the temperature became 50°C or less, immersed in 45 mass% hydrofluoric acid for 5 minutes, and the cured film of the resin composition was peeled off from the wafer. The film was cut into a long strip having a width of 1.5 cm and a length of 3 cm, and the dielectric constant and the dielectric loss tangent at a frequency of 1 GHz were measured at room temperature of 23.0°C and a humidity of 45.0% RH by the perturbation method cavity resonator method based on ASTM D2520. The dielectric properties were evaluated in five levels as in Table 1 below.

[0168] [Table 1]

[0169] Table 1

[0170]

[0171] (4) Measurement of elongation at break of cured film after curing

[0172] A self-supporting film of a cured film was produced in the same manner as in the above "(3) Measurement of dielectric constant, dielectric tangent", cut into a long strip of 1.5 cm in width and 9 cm in length, and the measurement of the elongation at break (%) was performed using a tensilon RTM-100 (manufactured by Orientec Corporation) at a tensile speed of 50 mm / min at a room temperature of 23.0°C and a humidity of 45.0% RH with stretching (gap between chucks = 2 cm). The measurement was performed on 10 pieces of the long strip per 1 sample, and the average value of the top 5 points with high values was calculated from the results (effective number of digits = 2 digits).

[0173] (5) Evaluation of elongation at break of cured film after high temperature storage (HTS)

[0174] After the varnish was applied on a 6-inch silicon wafer by a spin coating method using a coating and developing device MARK-7 so as to have a film thickness of 11 μm after pre-baking at 120°C for 3 minutes and pre-baking, exposure was performed using PLA at 300 mJ / cm 2 After the wafer was taken out when the temperature became 50°C or less, a high temperature storage tester was used to perform a 250-hour treatment at 150°C. The wafer was taken out, and a self-supporting film of a cured film was produced according to the steps after the hydrofluoric acid treatment described in the above "(3) Measurement of dielectric constant, dielectric tangent", and the evaluation of the elongation at break (%) was performed in the same manner as in "(4) Measurement of elongation at break of cured film after curing". The measurement was performed on 10 pieces of the long strip per 1 sample, and the average value of the top 5 points with high values was calculated from the results (effective number of digits = 2 digits).

[0175] Hereinafter, the abbreviations of the compounds used in the synthesis examples and the examples are described.

[0176] BPDA: 3,3',4,4'-diphenyltetracarboxylic dianhydride

[0177] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

[0178] 6FDA: 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride

[0179] BSAA: 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic acid) dianhydride

[0180] HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

[0181] DAE: 4,4'-diaminodiphenyl ether

[0182] TFMB: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,

[0183] Primene 1075: dimeric diamine compound containing the compound represented by the above formula (4) (trade name, manufactured by Croda Japan KK) (average amine value: 205)

[0184] Versamine 551: dimeric diamine compound containing the compound represented by the above formula (5) (trade name, manufactured by BASF) (average amine value: 205)

[0185] 6FAP: bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0186] DACH: diaminocyclohexane

[0187] MAP: m-aminophenol

[0188] NCI-831: oxime ester-based photopolymerization initiator (trade name, manufactured by ADEKA)

[0189] IRGANOX 3114: hindered phenol-based antioxidant (trade name, manufactured by BASF)

[0190] 4G: tetraethylene glycol dimethacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0191] DCP-A: dicyclopentadiene dimethacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)

[0192] HEMA: 2-hydroxyethyl methacrylate

[0193] OA: oleyl alcohol

[0194] DMM: dimethylaminoethyl methacrylate

[0195] NMP: N-methyl-2-pyrrolidone

[0196] EL: ethyl lactate

[0197] CP: cyclopentanone

[0198] PGMEA: propylene glycol methyl ether acetate

[0199] Polyflow 77: acrylic surfactant (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)

[0200] Diamine A: compound of the following structure

[0201]

[0202] [Synthesis of polyimide precursor (P-1)]

[0203] ODPA 31.02 g (0.10 mol) was charged into a 500 ml capacity separable flask, HEMA 26.03 g (0.20 mol) and NMP 123 ml were added, and triethylamine 22.26 g (0.22 mol) was added while stirring at room temperature to obtain a reaction mixture. After the heat generation caused by the reaction ended, it was allowed to cool to room temperature and left for 16 hours.

[0204] Next, the temperature was raised to 40°C, and (2,3-dihydro-2-thioxo-3-benzothiazolyl) diphenylphosphonate 76.7 g (0.2 mol) was added to the reaction mixture and stirred for 30 minutes. Next, a solution of Primal 1075 52.51 g (0.192 mol as amino group) in NMP 130 mL was added dropwise over 10 minutes while stirring. After further stirring at room temperature for 2 hours, MAP 0.87 g (0.008 mol) was added and stirred for 1 hour to obtain a reaction solution.

[0205] The obtained reaction solution was allowed to cool to room temperature, 3 L was added, and a precipitate formed by the crude polymer was generated. This precipitate was collected by filtration, washed with water 3 times, washed with isopropyl alcohol 500 mL twice, and vacuum dried to obtain a polyimide precursor (P-1) in powder form. The molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (converted to standard polystyrene), and the result was a weight average molecular weight (Mw) of 18000 and a PDI of 2.4.

[0206] [Synthesis Examples 2 to 14, 16]

[0207] Polyimide precursors (P-2) to (P-14) and (P-16) were synthesized by the same operation as in Synthesis Example 1 in the molar ratios shown in Table 2 below.

[0208] [Table 2]

[0209]

[0210] [Synthesis of polyimide precursor (P-15)]

[0211] ​BSAA 52.05 g (0.10 mol) was dissolved in NMP 250 g under a stream of dry nitrogen. Prøamin 1075 16.41 g (0.06 mol as amino group) and TFMB 21.14 g (0.066 mol) were added thereto together with NMP 100 g, and allowed to react at 20°C for 1 hour and then at 50°C for 2 hours. Next, 3-aminophenol 0.87 g (0.08 mol) as a capping agent was added together with NMP 30 g, and allowed to react at 50°C for 2 hours. Then, the temperature was returned to room temperature, DMM 31.44 g was added, and stirring was performed for 30 minutes to obtain a reaction solution. Further dilution with NMP until the solid content concentration became 25% gave a solution of polyimide precursor (P-15). Since the molecular weight of the polyimide precursor (P-15) could not be accurately measured, the molecular weight of the polymer before the DMM reaction was measured by gel permeation chromatography (conversion to standard polystyrene), and the result was Mw34000, PDI 2.8.

[0212] [Example 1]

[0213] A varnish was obtained by dissolving polyimide precursor (P-1) 10.00 g, NCI-831 0.5 g, IRGANOX 3114 0.10 g, 3-trimethoxysilyl anthranilic acid 0.30 g in NMP 15.15 g and EL 3.81 g, adding 1 mass% EL solution of Polyflow 77 0.10 g, and stirring under a yellow lamp. For the properties of the obtained varnish, the pattern processability, dielectric constant, dielectric loss tangent, and elongation at break were measured by the above evaluation methods.

[0214] [Example 2]

[0215] P-1 was replaced by P-2, and otherwise, the same as Example 1 was performed.

[0216] [Example 3]

[0217] P-1 was replaced by P-3, and otherwise, the same as Example 1 was performed.

[0218] [Example 4]

[0219] P-1 was replaced by P-4, and otherwise, the same as Example 1 was performed.

[0220] [Example 5]

[0221] P-1 was replaced by P-5, and otherwise, the same as Example 1 was performed.

[0222] [Example 6]

[0223] P-1 is replaced by P-6, and otherwise, the same as in Example 1 is carried out.

[0224] [Example 7]

[0225] P-1 is replaced by P-7, and otherwise, the same as in Example 1 is carried out.

[0226] [Example 8]

[0227] P-1 is replaced by P-8, and otherwise, the same as in Example 1 is carried out.

[0228] [Example 9]

[0229] P-1 is replaced by P-9, and otherwise, the same as in Example 1 is carried out.

[0230] [Example 10]

[0231] P-1 is replaced by P-10, and otherwise, the same as in Example 1 is carried out.

[0232] [Example 11]

[0233] P-1 is replaced by P-11, and otherwise, the same as in Example 1 is carried out.

[0234] [Example 12]

[0235] P-1 is replaced by P-12, and otherwise, the same as in Example 1 is carried out.

[0236] [Example 13]

[0237] Under a yellow lamp, 0.5 g of NCI-831, 0.10 g of IRGANOX 3114, and 0.30 g of 3-trimethoxysilyl anthranilic acid were dissolved in 40.00 g of a solution of the polyimide precursor (P-13) synthesized in Synthesis Example 13. Next, 0.10 g of a 1 mass% EL solution of Polyflow 77 was added, and stirring was performed to obtain a varnish. For the properties of the obtained varnish, the pattern processability, the dielectric constant, the dielectric loss tangent, and the elongation at break were measured by the above evaluation methods. Among these, as the developing solution, a mixed solution of NMP / PGMEA / water = 8 / 1 / 1 (by mass) was used, and isopropyl alcohol was used as the post-development rinsing solution.

[0238] [Example 14]

[0239] P-1 is replaced by P-9, and further, 0.2 g of 4G is added, and otherwise, the same as in Example 1 is carried out.

[0240] [Example 15]

[0241] P-1 was replaced by P-9, and DCP-A 0.2 g was further added, and otherwise, the same as Example 1 was carried out.

[0242] [Comparative Example 1]

[0243] P-1 was replaced by P-13, and otherwise, the same as Example 1 was carried out.

[0244] The composition and evaluation results of the examples and comparative examples are shown in Tables 3 and 4 below.

[0245] [Table 3]

[0246] Table 3

[0247]

[0248] [Table 4]

[0249] Table 4

[0250]

[0251] Explanation of Symbols

[0252] 1 Silicon wafer

[0253] 2 Al pad

[0254] 3 Passivation film

[0255] 4 Insulating film

[0256] 5 Metal (Cr, Ti, etc.) film

[0257] 6 Metal wiring (Al, Cu, etc.)

[0258] 7 Insulating film

[0259] 8 Barrier metal

[0260] 9 Dicing street

[0261] 10 Solder bump

[0262] 31 Antenna portion

[0263] 32 Matching circuit

[0264] 33 MSL feed line

[0265] 34 Feed point

[0266] 35 Ground

[0267] 36 Insulating film

[0268] J Ground thickness

[0269] K Antenna wiring thickness

[0270] M matching circuit length

[0271] L antenna portion length

[0272] W antenna portion width

[0273] 401 IC chip

[0274] 402 electrode pad

[0275] 403 2nd via wiring

[0276] 404 planar antenna wiring

[0277] 405 2nd sealing resin

[0278] 406 ground

[0279] 407 1st via wiring

[0280] 408 1st sealing resin

[0281] 409 copper wiring

[0282] 410 insulating film

[0283] 411 barrier metal

[0284] 412 solder bump

Claims

1. A photosensitive resin composition comprising (A) a polyimide precursor comprising a resin having a structural unit represented by General Formula (1), and (B) a photopolymerization initiator, wherein the (A) polyimide precursor comprises a resin having a structural unit represented by General Formula (11), In general formula (11), X 4 represents a 4- to 6-valent organic group, Y 4 represents a 2- to 6-valent organic group, wherein, X 4 and Y 4 at least one of X 8 each independently represents a monovalent organic group having an olefinic unsaturated bond or a hydrogen atom, wherein at least one of X 8 at least one of X 9 each independently represents a carboxyl group, a hydroxyl group or a monovalent organic group having an olefinic unsaturated bond; y represents an integer of 0 to 4; * represents a bonding point, In the general formula (11), Y 4 is a residue of a polyamine represented by the general formula (2), in General Formula (2), m represents any one of integers from 4 to 8; each of W independently represents any one of structural units represented by General Formulae (2a), (2b), and (2c), 2 or more of the structural units (2c) are contained among m W, and the sum of the numbers of (2b) and (2c) is 4 or more and 8 or less; each of n and o independently represents any one of integers from 3 to 11.

2. A photosensitive resin composition comprising (A) a polyimide precursor comprising a resin having a structural unit represented by General Formula (1), and (B) a photopolymerization initiator, In general formula (1), X 1 represents a 4- to 6-valent organic group, Y 1 represents a 2- to 6-valent organic group, wherein, X 1 and Y 1 at least any one of X and Y has an alicyclic hydrocarbon structure having 4 to 8 carbon atoms which can have an unsaturated bond, in which at least 4 or more hydrogen atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms which can have an unsaturated bond; a plurality of R 1 which can be the same or different, represents a monovalent organic group having an olefinic unsaturated bond or a hydrogen atom, wherein not all of R 1 are hydrogen atoms; p represents an integer of 2 to 4; a plurality of R 2 which can be the same or different, represents a carboxyl group, a hydroxyl group, or a monovalent organic group having an olefinic unsaturated bond; q represents an integer of 0 to 4; and * represents a bonding point.

3. The photosensitive resin composition according to claim 2, in the general formula (1), Y 1 is a residue of a polyamine represented by general formula (2) in General Formula (2), m represents any one of integers from 4 to 8; each of W independently represents any one of structural units represented by General Formulae (2a), (2b), and (2c), 2 or more of the structural units (2c) are contained among m W, and the sum of the numbers of (2b) and (2c) is 4 or more and 8 or less; each of n and o independently represents any one of integers from 3 to 11.

4. The photosensitive resin composition according to any one of claims 1 to 3, in the general formula (1), Y 1 is a residue of a diamine represented by formula (4), or in the general formula (11), Y 4 is a residue of a diamine represented by formula (4), 5. The photosensitive resin composition according to any one of claims 1 to 3, in the general formula (1), R 1 is a residue of an unsaturated fatty acid-modified alcohol, or in the general formula (11), R 8 is a residue of an unsaturated fatty acid-modified alcohol.

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) polyimide precursor comprises a resin having a structural unit represented by General Formula (1) and a structural unit represented by General Formula (7), or the (A) polyimide precursor comprises a resin having a structural unit represented by General Formula (11) and a structural unit represented by General Formula (7), In general formula (7), X 2 represents a 4- to 6-valent organic group, Y 2 represents a 2- to 6-valent organic group, wherein, at least X 2 is X 3 or Y 2 is Y 3 , X 3 is selected from the group consisting of a 2-6 valent organic group having any one or more of a bisphenol A skeleton, a biphenyl skeleton and a hexafluoroisopropylidene skeleton, or a residue of an acid anhydride represented by the following general formula (8), Y 3 is selected from the group consisting of a 2-6 valent organic group having any one or more of a bisphenol A skeleton, a biphenyl skeleton and a hexafluoroisopropylidene skeleton, or a residue of a diamine represented by the following formula (9); a plurality of R 3 may be the same or different, and represents a 1 valent organic group having an ethylenic unsaturated bond or a hydrogen atom, wherein not all of the R 3 are hydrogen atoms; r represents an integer of 2-4; a plurality of R 4 may be the same or different, and represents a carboxyl group, a hydroxyl group or a 1 valent organic group having an ethylenic unsaturated bond; s represents an integer of 0-4; * represents a bonding point, in General Formula (8), a represents an integer from 6 to 20; and * represents a bonding point. H2N-Y 4 -NH2 (9) in General Formula (9), * represents a bonding point.

7. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (C) a compound having 2 or more ethylenic unsaturated bonds, wherein the (C) component has a molecular weight of 100 or more and 2000 or less.

8. The photosensitive resin composition according to claim 7, wherein the (C) component is a compound having an alicyclic structure.

9. A photosensitive sheet formed from the photosensitive resin composition according to any one of claims 1 to 8.

10. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive sheet according to claim 9.

11. A method for producing a cured film, which is a method for producing a cured film using the photosensitive resin composition according to any one of claims 1 to 8 or the photosensitive sheet according to claim 9, comprising the following steps: a step of applying the photosensitive resin composition on a substrate or laminating the photosensitive sheet on a substrate, and drying to form a photosensitive resin film; a step of exposing the photosensitive resin film; a step of developing the exposed photosensitive resin film; and a step of heat treating the developed photosensitive resin film.

12. An interlayer insulating film provided with the cured film according to claim 10.

13. An electronic component having the cured film according to claim 10. ​ 14. The electronic component according to claim 13, which is an electronic component at least containing an antenna element, the antenna element being provided with one or more antenna wires, and the cured film according to claim 10, the antenna wires containing one or more selected from a meander-shaped loop antenna, a coil-shaped loop antenna, a meander-shaped monopole antenna, a meander-shaped dipole antenna, and a planar antenna, the area of each of the antenna portions of the antenna wires being 1000 mm2 or more. 2 Hereinafter, the cured film is an insulating film for insulating the ground from the antenna wires.

15. The electronic component according to claim 13 or 14, which is an electronic component containing at least a semiconductor package provided with a semiconductor element, a rewiring layer, a sealing resin, and an antenna wiring, the insulating layer of the rewiring layer and / or the sealing resin containing the cured film according to claim 10, the sealing resin also functioning as an insulating film for insulating the ground from the antenna wiring.

Images