Photosensitive resin composition, cured film, electronic component, antenna element, semiconductor package, and compound

Abstract

The purpose of the present invention is to provide a photosensitive resin composition and compound having a low dielectric loss tangent when made into a cured film. The present invention is a photosensitive resin composition containing (A) a polyfunctional monomer, (B) a binder resin, and (C) a photopolymerization initiator, the (A) polyfunctional monomer containing a compound represented by formula (1) and / or a compound represented by formula (2), and the (B) binder resin containing one or more substances selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamides, copolymers thereof, polyureas, polyesters, polysiloxanes, acrylic resins, phenol resins and benzocyclobutene resins, and maleic acid resins and cycloolefin polymers.

Description

Photosensitive resin composition, cured film, electronic component, antenna element, semiconductor package and compound

[0001] The present invention relates to a photosensitive resin composition, a cured film, an electronic component, an antenna element, a semiconductor package, and a compound. More specifically, the present invention relates to a photosensitive resin composition suitable for use as a surface protective film or interlayer insulating film for electronic components such as semiconductor elements, an insulating layer for organic electroluminescent devices, and the like.

[0002] Typical materials for surface protection films and interlayer insulating films of semiconductor elements, insulating layers of organic electrolytic elements, and planarizing films of TFT substrates include polyimide resins, which have excellent heat resistance and electrical insulation properties. Furthermore, to improve productivity, studies are being conducted on polyimides and their precursors that have been given negative or positive photosensitivity.

[0003] In recent years, efforts to reduce costs and increase integration by streamlining manufacturing processes have been underway in response to the expansion of semiconductor applications and improved performance. Therefore, semiconductor devices incorporating multilayer metal rewiring have attracted attention. The insulating films for such multilayer metal rewiring require multiple high-temperature processes during the manufacturing process. Furthermore, photolithographic patterning is required to improve productivity. Furthermore, in high-frequency communication device applications for high-speed wireless communication, a reduced dielectric loss tangent is required for insulating films to reduce transmission loss. Therefore, high mechanical properties, heat resistance, patternability, and low dielectric loss tangent are required. Examples of insulating films with sufficient heat resistance include resin compositions containing resins such as polyimide and polybenzoxazole and a thermal crosslinker (Patent Document 1). A method for imparting patternability is to use polyimide precursors with specific chemical structures introduced into the side chains (Patent Document 2).

[0004] JP 2007-16214 A JP 2011-59656 A

[0005] When conventional techniques were applied to a multilayer wiring insulating film for a high-frequency communication device for high-speed wireless communication, for example, in the case of a cured film of the composition described in Patent Documents 1 and 2, the reduction in dielectric loss tangent was insufficient.

[0006] In order to solve the above problems, the present invention relates to the following.

[0007] A photosensitive resin composition comprising (A) a polyfunctional monomer, (B) a binder resin, and (C) a photopolymerization initiator, wherein the (A) polyfunctional monomer comprises a compound represented by formula (1) and / or a compound represented by formula (2), and the (B) binder resin comprises one or more members selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, copolymers thereof, polyurea, polyester, polysiloxane, acrylic resin, phenolic resin, benzocyclobutene resin, maleic acid resin, and cycloolefin polymer.

[0008]

[0009] In formula (1), W １ and W ２ each independently represents a monovalent organic group having a carbon-carbon double bond and 2 to 25 carbon atoms. In formula (1), a, b, c, and d each independently represent natural numbers satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0010]

[0011] In formula (2), W ３ and W ４ each independently represents a monovalent organic group having a carbon-carbon double bond and 2 to 25 carbon atoms. In formula (2), e, f, g, and h each independently represent natural numbers satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0012] In another aspect for solving the above problems, the present invention relates to the following.

[0013] A compound represented by formula (1) or a compound represented by formula (2):

[0014]

[0015] In formula (1), W １ and W２ each independently represents a group represented by formula (3) or formula (4). In formula (1), a, b, c, and d each independently represent natural numbers satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0016]

[0017] In formula (2), W ３ and W ４ each independently represents a group represented by formula (3) or formula (4). In formula (2), e, f, g, and h each independently represent natural numbers satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0018]

[0019] In formula (3) and formula (4), X and Y represent —NH—. １ represents a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. ２ represents a single bond or a divalent organic group having 1 to 5 carbon atoms. i represents an integer of 1 to 5. * represents a bonding point.

[0020] A cured film of the photosensitive resin composition of the present invention and a cured film of a composition containing the compound of the present invention have an excellent low dielectric loss tangent.

[0021] Schematic of a coplanar-fed microstrip antenna Schematic of a cross section of a semiconductor package

[0022] The photosensitive resin composition of the present invention contains (A) a polyfunctional monomer (hereinafter may be abbreviated as component (A)), (B) a binder resin (hereinafter may be abbreviated as component (B)), and (C) a photopolymerization initiator (hereinafter may be abbreviated as component (C)), wherein the component (A) contains a compound represented by formula (1) and / or a compound represented by formula (2), and the component (B) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, copolymers thereof, polyurea, polyester, polysiloxane, acrylic resin, phenolic resin, benzocyclobutene resin, maleic acid resin, and cycloolefin polymer.

[0023]

[0024] In formula (1), W １ and W ２ each independently represents a monovalent organic group having a carbon-carbon double bond and 2 to 25 carbon atoms. In formula (1), a, b, c, and d each independently represent natural numbers satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0025]

[0026] In formula (2), W ３ and W ４ each independently represents a monovalent organic group having a carbon-carbon double bond and 2 to 25 carbon atoms. In formula (2), e, f, g, and h each independently represent natural numbers satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0027] The photosensitive resin composition of the present invention contains component (A). By including component (A), component (C) undergoes a crosslinking reaction with active species generated by exposure, thereby obtaining a negative pattern. Furthermore, the cured film obtained by curing the photosensitive composition has a low dielectric constant and a low dielectric loss tangent.

[0028] The component (A) contains a compound represented by formula (1) and / or a compound represented by formula (2). The compound represented by formula (1) and / or the compound represented by formula (2) is a photopolymerizable monomer obtained by reacting a dimer acid or a derivative thereof with a compound having a carbon-carbon double bond.

[0029] Dimer acids are known dibasic acids obtained by intermolecular polymerization of unsaturated fatty acids, and are obtained by dimerizing unsaturated fatty acids having 11 to 22 carbon atoms. Industrially obtained dimer acids are mainly composed of dibasic acids having 36 carbon atoms, which are obtained by dimerizing unsaturated fatty acids having 18 carbon atoms, such as oleic acid and linoleic acid, but may contain arbitrary amounts of monomeric acids having 18 carbon atoms, trimer acids having 54 carbon atoms, and other polymerized fatty acids having 20 to 54 carbon atoms, depending on the degree of purification.

[0030] Examples of dimer acid derivatives include dimer diols in which all carboxyl groups of the dimer acid are replaced with primary hydroxyl groups, dimer diamines in which all carboxyl groups are replaced with primary amino groups, dimer thiols in which all carboxyl groups are replaced with primary thiol groups, and dimer isocyanates in which all carboxyl groups are replaced with isocyanate groups.Furthermore, examples of dimer acid derivatives include epoxy compounds and oxetane compounds obtained by reaction of these functional groups.

[0031] The compound having a carbon-carbon double bond further contains one functional group capable of reacting with a dimer acid derivative. Specific examples of the functional group include an amino group, a hydroxy group, a carboxyl group or a substituent of a salt thereof, an epoxy group, an acid anhydride group, and an isocyanate group. The reaction of these functional groups with the functional groups of the dimer acid or its derivatives produces a compound represented by formula (1) and / or a compound represented by formula (2).

[0032] Specific examples of the compound having a carbon-carbon double bond include N-(4-aminophenyl)maleimide, 4-aminostyrene, 3-aminostyrene, 2-aminostyrene, 3-amino-1-propene, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2-propyl alcohol, 2-(meth)acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl propyl (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)acryloxyethyl-2-hydroxypropyl phthalate, 2-vinylbenzyl alcohol, 3-vinylbenzyl alcohol, 4-vinylbenzyl alcohol Alcohols having one ethylenically unsaturated bond and one hydroxyl group, such as ethanol, glycerin-1,3-di(meth)acrylate, glycerin-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin-1-allyloxy-3-methacrylate, glycerin-1-allyloxy-2-methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), 2-(acryloyl) alcohols having two or more ethylenically unsaturated bonds and one hydroxyl group, such as (hydroxymethyl)-2-(hydroxymethyl)butyl methacrylate, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and derivatives thereof, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, 4-pentene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate or 1,Examples include 1-(bisacryloyloxymethyl)ethyl isocyanate. Here, "(meth)acrylate" refers to methacrylate or acrylate. The same applies to similar notations.

[0033] Specific examples of commercially available dimer acids include Haridimer 200 and Haridimer 270S (all trade names, manufactured by Harima Chemicals Co., Ltd.), Td-205(W) and Td-395 (all trade names, manufactured by Tsuno Foods Industries Co., Ltd.), Pripol 1004, Pripol 1006, Pripol 1009, Pripol 1013, Pripol 1017 and Pripol 1040 (all trade names, manufactured by Croda Japan Co., Ltd.).

[0034] As dimer acid derivatives, commercially available dimer diol products include Pespol HP-1000 (trade name, manufactured by Toagosei Co., Ltd.) and Pripol 2023 (trade name, manufactured by Croda Japan Co., Ltd.). Commercially available dimer diamine products include Versamine 551 and Versamine 552 (both trade names, manufactured by BASF Japan Co., Ltd.), Priamine 1071, Priamine 1073, Priamine 1074, and Priamine 1075 (all trade names, manufactured by Croda Japan Co., Ltd.).

[0035] From the viewpoint of exposure sensitivity, W １ and W ２ At least one of the above and W ３ and W ４ At least one of the groups represented by formula (3), (4), (5) or (6) is preferably a group represented by formula (3), (4), (5) or (6).

[0036]

[0037]

[0038] In formula (3), formula (4), formula (5) and formula (6), X and Y each independently represent -NH-, -O-, -CH ２ - or -S-. １ represents a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. ２ represents a single bond or a divalent organic group having 1 to 5 carbon atoms. i represents an integer of 1 to 5. * represents a bonding point.

[0039] In the formula (1) and the formula (2), W １ and W ２ At least one of the above and W ３ and W ４ Specific examples of the component (A) in which at least one of the above is a group represented by formula (3), formula (4), formula (5) or formula (6) include formula (7).

[0040]

[0041] In addition, from the viewpoint of reducing the dielectric properties, W in the formula (1) and the formula (2) １ and W ２ At least one of the above and W ３ and W ４ At least one of the above is a group represented by formula (3) or formula (4), and in formula (3) and formula (4), X and Y are preferably —NH—.

[0042] In addition, in the formula (1) and the formula (2), W １ and W ２ At least one of the above and W ３ and W ４ It is more preferable that at least one of the groups is a group represented by formula (8), formula (9), formula (10) or formula (11).

[0043]

[0044]

[0045] * indicates the point of attachment.

[0046] The component (A) is preferably prepared in an amount within the range of 5% by mass to 50% by mass in the resin composition.

[0047] The method for producing component (A) is not particularly limited, and known synthesis methods such as addition reactions or condensation reactions can be used. An example of a specific production method is shown below. In the first step, a compound having a carbon-carbon double bond and one functional group capable of reacting with a dimer acid derivative is placed in a reaction vessel under a nitrogen atmosphere and stirred. If necessary, a solvent may be added, and a reaction catalyst or reaction accelerator may also be added. It is preferable to use a solvent with a solubility parameter of 10 or less according to the Fedor method. Specific examples include, but are not limited to, toluene and propylene glycol methyl ether acetate. Two or more solvents may also be used.

[0048] The reaction catalyst can be appropriately selected depending on the reaction to be applied, and in the case of a reaction between a carboxyl group and an epoxy group, examples include ammonium-based catalysts such as tetrabutylammonium acetate, amino-based catalysts such as dimethylbenzylamine, and phosphorus-based catalysts such as triphenylphosphine, and in the case of a reaction between an isocyanate group and an amino group or a hydroxyl group, examples include tin compounds such as dibutyltin dilaurate, or tertiary amines such as 1,4-dibicyclo[2.2.2]octane. The reaction accelerator is mainly required when the reaction to be applied is a condensation reaction between a carboxyl group and an amino group or a hydroxyl group, and examples include, but are not limited to, dicyclohexylcarbodiimide, diisopropylcarbodiimide, and the like.

[0049] In the second step, a dimer acid derivative is added dropwise to the stirred solution prepared in the first step, and the mixture is stirred until the reaction is complete. The commercially available dimer acid derivative is preferably used. If the reaction heat is large, cooling may be performed during the dropwise addition, as necessary. In the third step, after the reaction is complete, the solvent in the prepared solution is removed using an evaporator to obtain component (A). Furthermore, when a reaction catalyst or reaction accelerator is used, it is preferable to remove it by liquid separation or silica gel chromatography. The component (A) in the present invention can be identified using a nuclear magnetic resonance (NMR) spectrometer or the like.

[0050] NMR is an analytical method in which a sample is placed in a strong magnetic field, and pulsed radio waves are irradiated onto molecules with aligned spin directions, causing nuclear magnetic resonance. The signal generated when the molecules return to their original stable state is then detected, and molecular structure and other information are analyzed. The most commonly used NMR analysis is １ In H-NMR spectra, information about molecular structure can be obtained, such as the environment of the hydrogen atoms from the chemical shift of the peaks, the number of hydrogen atoms from the integral value, and the influence of neighboring protons from the peak splitting. Examples of characteristic chemical shifts include the chemical shift of hydrogen atoms bonded to allylic carbons at 1.5-2 ppm, the chemical shift of hydrogen atoms bonded to alkenes at 4.5-6 ppm, the chemical shift of hydrogen atoms bonded to aromatic rings at 6-9 ppm, and the chemical shift of hydrogen atoms bonded to amide groups at 5-11 ppm.

[0051] The photosensitive resin composition of the present invention contains component (B). By appropriately selecting component (B), it is possible to control the properties of the photosensitive resin composition and the properties of the cured film obtained by curing the photosensitive resin composition. Component (B) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, copolymers thereof, polyurea, polyester, polysiloxane, acrylic resin, phenolic resin, benzocyclobutene resin, maleic acid resin, and cycloolefin polymer. Here, unless otherwise specified, polyamide refers to polyamide other than polyimide precursor and polybenzoxazole precursor.

[0052] In particular, from the viewpoint of the heat resistance and mechanical properties of the cured film, the component (B) preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, and maleic acid resin. Also, the component (B) preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof.

[0053] Furthermore, it is more preferable that the component (B) contains at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof, which are obtained by polymerizing a dimer acid derivative as a monomer.

[0054] In addition, since development with an alkaline aqueous solution becomes possible, it is preferable to contain one or more polyimides selected from the group consisting of polyimide precursors and copolymers thereof, each having a phenolic hydroxyl group in an acid dianhydride residue or a diamine residue.

[0055] Furthermore, from the viewpoint of developability and low dielectric loss tangent, the component (B) more preferably contains a phenolic resin having a biphenyl structure, which is a rigid structure. A plurality of these resins may be used in combination.

[0056] Examples of polyimide precursors include those obtained by reacting tetracarboxylic acids and their derivatives with diamines and their derivatives, and examples of polyimide precursors include polyamic acids, polyamic acid esters, polyamic acid amides, and polyisoimides.

[0057] Examples of tetracarboxylic acids and derivatives thereof include 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2 ,2',3,3'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 2,2-bis(3 ,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 2,3,5,6-pyridinetetracarboxylic acid or 3,4,9,10-perylenetetracarboxylic acid, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3,4-dicarboxybenzoic acid amine tetracarboxylic acid), bicyclo[2.2.2]octan-7-ene-2,3,5,6-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, or a tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride, or tetracarboxylic acid activated diester thereof. These compounds may be used alone or in combination of two or more.

[0058] Examples of diamines and derivatives thereof include m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl, bis(4-aminophenoxy)biphenyl, 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, 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, dimercaptophenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-amino phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, 2,7-diaminofluorene, 9,9-bis(4-amino nophenyl)fluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisil Examples include cyclohexane, ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and dimer diamine. Dimer diamine is particularly preferred from the viewpoint of reducing the dielectric loss tangent.

[0059] In addition, in applications requiring alkali solubility, bisaminophenol compounds are preferred. Examples of bisaminophenol compounds include bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, 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(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, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 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)-3,3'-diamino-4,4 -dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane.

[0060] Furthermore, examples of diamines having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane, which are preferred because they can improve adhesion to the substrate.

[0061] The polyamine compounds may be used as they are or after the amine moiety is isocyanated or trimethylsilylated. Two or more of these polyamine compounds may also be used in combination.

[0062] Furthermore, the weight average molecular weight of the resin can be adjusted by capping the resin terminals with a monoamine, an acid anhydride, an acid chloride, or a monocarboxylic acid.

[0063] Preferred examples of monoamines include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. , 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used.

[0064] Preferred examples of the acid anhydride, acid chloride, and monocarboxylic acid include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, and 1-mercapto-5-carboxynaphthalene. Examples of such compounds include monocarboxylic acids such as 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene, and monoacid chloride compounds in which only one carboxyl group of such dicarboxylic acids is converted to an acid chloride; and activated ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these compounds may be used.

[0065] Examples of polyimides include those obtained by dehydrating and ring-closing the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide by heating or by a reaction using an acid, a base, or the like, and have residues of tetracarboxylic acid and / or a derivative thereof and residues of diamine and / or a derivative thereof.

[0066] A polyimide precursor is a thermosetting resin that is thermally cured at high temperatures to undergo dehydration and ring closure, thereby forming highly heat-resistant imide bonds and obtaining a polyimide. Therefore, by incorporating a polyimide having highly heat-resistant imide bonds into a resin composition, the heat resistance of the resulting cured film can be significantly improved. Therefore, the polyimide precursor is suitable for use in applications requiring high heat resistance. Furthermore, since the polyimide precursor is a resin whose heat resistance improves after dehydration and ring closure, it is suitable for use in applications requiring both the properties of the precursor structure before dehydration and ring closure and the heat resistance of the cured film.

[0067] The polyimide may, for example, be a polyimide containing a structural unit represented by the following formula (12):

[0068]

[0069] In formula (12), R ４ represents a tetravalent to decavalent organic group, and R ５ represents a divalent to octavalent organic group. ６ and R ７ represents a hydroxyl group or an organic group having 1 to 20 carbon atoms, and may be a single group or a mixture of different groups. j and k represent integers of 0 to 6. R ４ - (R ６ ) ｊ represents the residue of the above-mentioned tetracarboxylic acid and / or its derivative. ５ - (R ７ ) ｋ indicates the residue of the above-mentioned diamine and / or its derivative. Dimer diamine residues are particularly preferred from the viewpoint of achieving a low dielectric loss tangent. * indicates a bonding point.

[0070] The polyimide precursor is preferably a polyamic acid or a polyamic acid ester, and examples thereof include polyimide precursors containing a structural unit represented by formula (13).

[0071]

[0072] In formula (13), R ８ represents a tetravalent to hexavalent organic group, R ９ represents a divalent to decavalent organic group. １１each independently represents an organic group having 1 to 10 carbon atoms or a hydroxyl group, and n represents an integer of 0 to 8. １０ may be the same or different and represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. m represents an integer of 2 to 4. ８ -(COOR １０ ) ｍ represents the residue of the above-mentioned tetracarboxylic acid and / or its derivative. ９ - (R １１ ) ｎ indicates the residue of the aforementioned diamine and / or its derivative. Dimer diamine residue is particularly preferred from the viewpoint of achieving a low dielectric loss tangent. Furthermore, from the viewpoint of solubility in alkaline aqueous solutions, bisaminophenol residues are preferred, with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane residue or 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane residue being particularly preferred. * indicates a bonding point.

[0073] Also R １０ When R represents an organic group having 1 to 30 carbon atoms, １０Specifically, represents a tetracarboxylic acid diester residue. Tetracarboxylic acid diesters can be produced by reacting an acid dianhydride and an alcohol directly in a solvent. However, from the perspective of reactivity, it is preferable to use a reaction activator. Examples of reaction activators include tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine, and 1,8-diazabicycloundecene. The amount of reaction activator added is preferably 3 mol% to 300 mol%, more preferably 20 mol% to 150 mol%, based on the acid anhydride groups to be reacted. A small amount of a polymerization inhibitor may be used to prevent crosslinking of ethylenically unsaturated bond sites during the reaction. This allows the reaction between an alcohol having a low reactivity ethylenically unsaturated bond and a tetracarboxylic acid dianhydride to be accelerated by heating at a temperature of 120°C or less. Examples of polymerization inhibitors include phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. The amount of the polymerization inhibitor to be added is preferably such that the amount of the phenolic hydroxyl group in the polymerization inhibitor is 0.1 mol % or more and 5 mol % or less relative to the ethylenically unsaturated bond of the alcohol.

[0074] Examples of the alcohols having an ethylenically unsaturated bond include (meth)acrylates having a hydroxyl group or unsaturated fatty acid modified alcohols. Examples of the (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2-propyl alcohol, 2-(meth)acrylamidoethyl alcohol, methylol 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, and 2-hydroxy-3-cyclohexyloxypropyl (meth)acrylate. and alcohols having two or more ethylenically unsaturated bonds and one hydroxyl group, such as glycerin-1,3-di(meth)acrylate, glycerin-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin-1-allyloxy-3-methacrylate, glycerin-1-allyloxy-2-methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), and 2-(acryloyloxy)-2-(hydroxymethyl)butyl methacrylate.

[0075] Examples of unsaturated fatty acid-modified alcohols include unsaturated fatty acid-modified alcohols having 6 or more carbon atoms. From the viewpoint of exposure sensitivity, alcohols having an unsaturated group at a terminal or a double bond with a cis structure are preferred, and from the viewpoint of dielectric constant and dielectric dissipation factor, alcohols having 12 or more carbon atoms are preferred. Specific examples of unsaturated fatty acid-modified alcohols include 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, elidolinoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and erucyl alcohol. Of these, oleyl alcohol, linoleyl alcohol, and linolenyl alcohol are preferred from the viewpoint of the dielectric properties and exposure sensitivity of the resulting cured film.

[0076] When reacting an acid anhydride with an alcohol having an ethylenically unsaturated bond, other alcohols may be used simultaneously, which can be appropriately selected depending on various purposes, such as adjusting exposure sensitivity or adjusting solubility in organic solvents. Specific examples include aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and i-pentanol; and monoalcohols derived from alkylene oxides such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and tripropylene glycol monobutyl ether.

[0077] Examples of polybenzoxazole precursors include polyhydroxyamides obtained by reacting dicarboxylic acids and derivatives thereof with diamines such as bisaminophenol compounds.

[0078] Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, dimer acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. These compounds may be used alone or in combination of two or more. Dimer acid is particularly preferred from the viewpoint of reducing the dielectric loss tangent. Examples of bisaminophenols include the bisaminophenol compounds exemplified in the polyimide precursor.

[0079] Polybenzoxazole precursors are thermosetting resins that undergo thermal curing at high temperatures to form highly heat-resistant and rigid benzoxazole rings, resulting in polybenzoxazole. Therefore, by incorporating polybenzoxazole having highly heat-resistant and rigid benzoxazole rings into a resin composition, the heat resistance of the resulting cured film can be significantly improved. This makes the cured film suitable for applications requiring high heat resistance. Furthermore, since the polybenzoxazole precursor is a resin whose heat resistance improves after dehydration and ring closure, it is suitable for applications requiring both the properties of the precursor structure before dehydration and ring closure and the heat resistance of the cured film.

[0080] Examples of polybenzoxazoles include those obtained by dehydrating and cyclizing a dicarboxylic acid and a bisaminophenol compound as a diamine through a reaction using polyphosphoric acid, and examples of polybenzoxazole precursors include those obtained by dehydrating and cyclizing the above-mentioned polyhydroxyamides through heating or a reaction using phosphoric anhydride, a base, a carbodiimide compound, or the like.

[0081] The polybenzoxazole may include those containing a structural unit represented by formula (14).

[0082]

[0083] In formula (14), R １２represents a divalent to hexavalent organic group, R １３ represents a tetravalent to hexavalent organic group. １４ and R １５ are each independently an organic group having 1 to 10 carbon atoms or a hydroxyl group, o is an integer of 0 to 4, and p is an integer of 0 to 2. １２ - (R １４ ) о represents the residue of the dicarboxylic acid and / or its derivative. In particular, a dimer acid residue is preferred from the viewpoint of achieving a low dielectric loss tangent. １３ - (R １５ ) ｐ indicates the residue of the above-mentioned bisaminophenol compound and / or its derivative. * indicates the point of attachment.

[0084] The polybenzoxazole precursor used in the present invention includes those containing a structural unit represented by the following formula (15).

[0085]

[0086] In formula (15), R １６ represents a divalent to hexavalent organic group, R １７ represents a single bond or a divalent to hexavalent organic group. １８ and R １９ represents an organic group having 1 to 10 carbon atoms or a hydroxyl group. q and r represent integers of 0 to 4. R １６ - (R １８ ) ｑ represents the residue of the dicarboxylic acid and / or its derivative. In particular, a dimer acid residue is preferred from the viewpoint of achieving a low dielectric loss tangent. １７ - (R １９ ) ｒ indicates the residue of the above-mentioned bisaminophenol compound and / or its derivative. * indicates the point of attachment.

[0087] Examples of polyamides include those obtained by dehydration condensation of a dicarboxylic acid and a diamine compound using polyphosphoric acid, and include those containing a structural unit represented by the following formula (16):

[0088]

[0089] In formula (16), R ２０ and R ２１ represents a divalent to hexavalent organic group. ２２ and R ２３ are each independently an organic group having 1 to 10 carbon atoms or a hydroxyl group, t is an integer of 0 to 4, and u is an integer of 0 to 4. R ２０ - (R ２２ ) ｔ represents the residue of the dicarboxylic acid and / or its derivative, and R ２１ - (R ２３ ) ｕ indicates a residue of a diamine compound and / or a derivative thereof, excluding the above-mentioned bisaminophenol compound. * indicates a bonding point.

[0090] The component (B) may also contain a copolymer of two or more members selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polyamide.

[0091] Examples of polyureas include those obtained by polyaddition reaction of diamines and polyfunctional isocyanates.

[0092] Examples of diamines include the compounds exemplified for polyimide, polybenzoxazole, and polyamide.

[0093] Examples of polyfunctional isocyanates include hexamethylene diisocyanate, 1,3-bis(isocyanatemethyl)benzene, 1,3-bis(isocyanatemethyl)cyclohexane, norbornene diisocyanate, naphthalene-1,5-disocyanate, diphenylmethane-4,4'-diisocyanate, and toluene-2,4-diisocyanate. Examples of polyols include ethylene glycol, propylene glycol, pentaerythritol, dipentaerythritol, 1,4-bis(2-hydroxyethoxy)benzene, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, and bis(4-(2-hydroxyethoxy)phenyl)methane. The polyaddition reaction product of diamine and polyfunctional isocyanate can be obtained without a catalyst, but a catalyst may also be used. The catalyst may be a tin compound such as dibutyltin dilaurate or a tertiary amine such as 1,4-diazabicyclo[2.2.2]octane.

[0094] As the polyester, those obtained by a polyaddition reaction between a polyol compound and an acid dianhydride are preferred because they are easy to synthesize and involve few side reactions. As the polyol compound, those obtained by a reaction between a polyfunctional epoxy compound and a monobasic acid compound containing a radical polymerizable group such as (meth)acrylic acid are preferred because they are easy to introduce a radical polymerizable group and an aromatic ring into.

[0095] Examples of polyfunctional epoxy compounds include, but are not limited to, aliphatic epoxy compounds such as ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, or hydrogenated bisphenol A diglycidyl ether, or aromatic epoxy compounds such as hydrogenated bisphenol A diglycidyl ether or 9,9-bis(4-glycidyloxyphenyl)fluorene.

[0096] Other examples of the polyol compound include aliphatic alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, and pentaerythritol, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene. Examples of the acid dianhydride include the tetracarboxylic acid dianhydrides exemplified in the description of the polyimide precursor.

[0097] The polysiloxane may be a hydrolysis condensate of at least one organosilane compound. Examples of the organosilane compound include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. xyloxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane Examples of the organosilanes include trifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, and di(1-naphthyl)diethoxysilane; and monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane. Two or more of these organosilanes may be used.

[0098] The hydrolysis reaction conditions for the organosilane compound may be set as appropriate, but it is preferable to add an acid catalyst and water to the organosilane compound in a solvent over 1 to 180 minutes, and then carry out the reaction at room temperature to 110°C for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is preferably 30 to 105°C.

[0099] The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. The acid catalyst is preferably an acidic aqueous solution containing formic acid, acetic acid, or phosphoric acid. The content of the acid catalyst is preferably 0.1 to 5 parts by mass per 100 parts by mass of all organosilane compounds used in the hydrolysis reaction. By setting the content of the acid catalyst within the above range, the hydrolysis reaction can be easily controlled so that it proceeds as needed and sufficiently.

[0100] As for the conditions for the condensation reaction, it is preferable to obtain a silanol compound by hydrolysis of the organosilane compound, and then heat the reaction solution as is at 50°C to the boiling point of the solvent for 1 to 100 hours. Furthermore, reheating or the addition of a base catalyst may be performed to increase the degree of polymerization of the polysiloxane. Furthermore, if necessary, after the hydrolysis reaction, an appropriate amount of the produced alcohol may be distilled and removed by heating and / or reduced pressure, and then an optional solvent may be added.

[0101] Examples of acrylic resins include those obtained by radical polymerization of (meth)acrylic acid and (meth)acrylic acid esters. Among these, carboxyl group-containing acrylic resins are preferred from the viewpoint of pattern processability, and it is preferred that at least a portion of the resin contains an ethylenically unsaturated double bond group from the viewpoint of hardness of the cured film.

[0102] The synthesis of acrylic resins can be achieved by radical polymerization of (meth)acrylic compounds. Examples of (meth)acrylic compounds include (meth)acrylic compounds containing carboxyl groups and / or acid anhydride groups, and other (meth)acrylic acid esters. Azo compounds such as azobisisobutyronitrile or organic peroxides such as benzoyl peroxide are commonly used as catalysts for radical polymerization.

[0103] The radical polymerization conditions may be set appropriately, but it is preferable to add a carboxyl group- and / or acid anhydride group-containing (meth)acrylic compound, other (meth)acrylic acid esters, and a radical polymerization catalyst to a solvent, thoroughly replace the atmosphere in a reaction vessel with nitrogen by bubbling or degassing under reduced pressure, and then carry out the reaction at 60 to 110°C for 30 to 300 minutes. When an acid anhydride group-containing (meth)acrylic compound is used, it is preferable to add a theoretical amount of water and carry out the reaction at 30 to 60°C for 30 to 60 minutes. Furthermore, a chain transfer agent such as a thiol compound may be used as needed.

[0104] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, and 2-cyclopentyloxycarbonylethyl (meth)acrylate. Examples of the acrylate include cyclohexyloxycarbonylethyl, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyladamantyl (meth)acrylate, and 1-methyladamantyl (meth)acrylate.

[0105] The acrylic resin may also be a copolymer of a (meth)acrylic compound and another unsaturated double bond-containing monomer. Examples of other unsaturated double bond-containing monomers include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, p-hydroxystyrene, maleic anhydride, norbornene, norbornene dicarboxylic acid, norbornene dicarboxylic acid anhydride, cyclohexene, butyl vinyl ether, butyl allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, and 4-hydroxybutyl vinyl ether.

[0106] The acrylic resin having an ethylenically unsaturated bond is preferably one obtained by radical polymerization of a carboxyl group- and / or acid anhydride group-containing (meth)acrylic compound, a (meth)acrylic acid ester, and / or other unsaturated double bond-containing monomer, followed by an addition reaction with an epoxy compound having an ethylenically unsaturated double bond. Catalysts used in the addition reaction include, for example, amino-based catalysts such as dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, and dimethylbenzylamine, phosphorus-based catalysts such as triphenylphosphine, ammonium-based catalysts such as tetrabutylammonium acetate, and chromium-based catalysts such as chromium acetylacetonate and chromium chloride.

[0107] Examples of epoxy compounds having an ethylenically unsaturated double bond group include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, α-n-propyl glycidyl (meth)acrylate, α-n-butyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, butyl vinyl ether, butyl allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl allyl ether, allyl glycidyl ether, vinyl glycidyl ether, and o-vinyl Examples thereof include benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, and 2,4,6-triglycidyloxymethylstyrene.

[0108] Phenol resins include novolak resins and resol resins, which are obtained by polycondensing various phenols alone or a mixture thereof with aldehydes such as formalin.

[0109] Examples of phenols constituting novolac resins and resol resins include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis-p-cresol, resorcinol, and carboxymethylphenol. Examples of suitable phenols include tetrachlorophenol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, p-phenylphenol, α-naphthol, and β-naphthol, which can be used alone or in combination.

[0110] In addition, examples of aldehydes that can be used for polycondensation with novolak resins or resol resins include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde, and these can be used alone or in combination.

[0111] The phenolic resin may also have a structure in which some of the hydrogen atoms attached to the aromatic ring are substituted with one or more of an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, a hydroxyl group, an alkoxyl group, an alkoxymethyl group, a methylol group, a carboxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

[0112] Particularly from the viewpoint of achieving low dielectric constant, novolac resins or resol resins having a rigid naphthalene structure or biphenyl structure are more preferred, and specifically, p-phenylphenol, α-naphthol, or β-naphthol is preferably used as the phenol. Commercially available phenolic resins include PN-80, PN-100, GPH-65, and GPH-103 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), XLC-3L (trade name, manufactured by Mitsui Chemicals, Inc.), and MEHC-7851SS (trade name, manufactured by Meiwa Kasei Co., Ltd.), with GPH-65, GPH-103, and MEHC-7851SS having a rigid structure being particularly preferred.

[0113] Benzocyclobutene resins are produced, for example, by reacting a brominated arylcyclobutene compound with a compound containing an unsaturated alkyl group in the presence of a palladium catalyst. Specific examples include divinylsiloxane bisbenzocyclobutene. Commercially available benzocyclobutene compounds include CYCLOTENE 3022-63 and 4026-46 (trade names, manufactured by The Dow Chemical Company).

[0114] Maleic acid resins are produced, for example, by copolymerizing maleic anhydride or a maleic acid ester with a compound containing an unsaturated alkyl group in the presence of a radical polymerization catalyst. Specific examples include styrene-maleic anhydride copolymers and maleic anhydride-modified polyethylene. Commercially available maleic acid resins include XIRAN 1000, XIRAN 1440, XIRAN 2000, XIRAN 2500, XIRAN 3000, XIRAN 3500, XIRAN 4000, XIRAN 6000, and XIRAN 9000 (all trade names, manufactured by Tomoe Engineering Co., Ltd.).

[0115] Cycloolefin polymers are produced, for example, by hydrogenation ring-opening metathesis polymerization of norbornene, or by addition polymerization of norbornene and an unsaturated alkyl group-containing compound in the presence of a radical polymerization catalyst, followed by hydrogenation. Commercially available products include the APL series (trade name, Mitsui Chemicals, Inc.).

[0116] In the resin composition, the content of component (B) is preferably 10 parts by mass or more per 100 parts by mass of component (A) to form a coating film with a thickness of 1 μm or more, and is preferably 500 parts by mass or less to sufficiently reduce the dielectric loss tangent of the resulting cured film.

[0117] The photosensitive resin composition of the present invention contains component (C). By including component (C), active species that initiate a crosslinking reaction of component (A) are generated upon exposure, enabling pattern processing through a subsequent development step. Component (C) is not particularly limited as long as it is a compound that generates radicals upon exposure, but alkylphenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, oxime ester compounds, and benzoic acid ester compounds are preferred due to their excellent sensitivity, stability, and ease of synthesis. Among these, alkylphenone compounds and oxime ester compounds are preferred from the viewpoint of sensitivity, with oxime ester compounds being particularly preferred. Furthermore, when the processed film thickness is 5 μm or greater, phosphine oxide compounds are preferred from the viewpoint of resolution.

[0118] The alkylphenone compound may contain known compounds, for example, α-aminoalkylphenone compounds such as 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, α-hydroxyalkylphenone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, α-alkoxyalkylphenone compounds such as 4-benzoyl-4-methylphenyl ketone, and acetophenone compounds such as p-t-butyldichloroacetophenone.

[0119] Among these, α-aminoalkylphenone compounds such as 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 are preferred because of their high sensitivity.

[0120] The phosphine oxide compound may contain known compounds, such as 6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide.

[0121] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), NCI-831, NCI-930 (all manufactured by ADEKA Corporation), OXE-03, OXE-04 (all manufactured by BASF Corporation), and the like.

[0122] Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], NCI-831, NCI-930, OXE-03, and OXE-04 are preferred from the viewpoint of sensitivity.

[0123] The aminobenzophenone compound may contain known compounds, such as 4,4-bis(dimethylamino)benzophenone. Examples of the diketone compound include known compounds such as benzil. Examples of the ketoester compound include known compounds such as methyl benzoylformate and ethyl benzoylformate.

[0124] Examples of the benzoic acid ester compound include known compounds such as methyl o-benzoylbenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4-(dimethylamino)benzoate.

[0125] Other specific examples of the component (C) include known compounds such as triphenylphosphine, carbon tetrabromide, and tribromophenyl sulfone.

[0126] The content of component (C), relative to 100 parts by mass of the sum of components (A) and (B), is preferably 0.5 parts by mass or more and 20 parts by mass or less, since sufficient sensitivity can be obtained and the amount of degassing during thermal curing can be suppressed, and more preferably 1.0 part by mass or more and 10 parts by mass or less.

[0127] A sensitizer may be contained to enhance the functionality of component (C). The inclusion of a sensitizer makes it possible to improve sensitivity and adjust the photosensitive wavelength. Known sensitizers can be contained. Examples of sensitizers that can be used include, but are not limited to, bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine, and derivatives thereof.

[0128] The photosensitive resin composition of the present invention preferably further contains a (D) crosslinking agent (hereinafter sometimes abbreviated as "component (D)"). Component (D) is a compound having a functional group that crosslinks when heated, and specific examples of the functional group include an epoxy group, an oxetane group, and a methylol group. Component (D) preferably contains one or more compounds selected from the group consisting of epoxy compounds, oxetane compounds, and methylol compounds, and more preferably contains a methylol compound from the viewpoint of reducing the dielectric constant and dielectric loss tangent.

[0129] Known epoxy compounds may be contained, for example, Epolite (registered trademark) 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L (all trade names, manufactured by Nagase ChemteX Corporation), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, E4275 (all trade names, manufactured by Japan Epoxy Resins Co., Ltd.), Examples of such an ink include Epiclon EXA-9583, Epiclon N695, HP4032, and HP7200 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), VG3101 (trade name, manufactured by Mitsui Chemicals, Inc.), Tepic S, Tepic G, and Tepic P (trade names, manufactured by Nissan Chemical Industries, Ltd.), Epotohto YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), GAN, GOT, EPPN502H, NC3000, and NC6000 (trade names, manufactured by Nippon Kayaku Co., Ltd.).

[0130] Known oxetane compounds may be contained, for example, OXT-101, OXT-121, OXT-212, and OXT-221 (all trade names, manufactured by Toagosei Co., Ltd.), Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, Ethanacol OXMA, and Ethanacol OXIPA (all trade names, manufactured by Ube Industries, Ltd.), and oxetanized phenol novolak.

[0131] Known methylol compounds can be contained, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, T riML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM- BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKALAC (registered trademark) Examples of suitable acrylic resins include NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (all of which are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0132] From the viewpoint of obtaining high chemical resistance of the cured film and reducing the dielectric constant and dielectric dissipation factor, the content of the component (D) is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the total amount of the component (A).

[0133] The photosensitive resin composition may contain a solvent. Examples of the solvent include 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-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

[0134] The content of the solvent is preferably 100 parts by mass or more per 100 parts by mass of component (A) in order to dissolve the composition, and is preferably 1,500 parts by mass or less in order to form a coating film with a thickness of 1 μm or more.

[0135] The photosensitive resin composition may contain known antioxidants, surfactants, and adhesion improvers.

[0136] The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.

[0137] A cured film can be obtained by applying a photosensitive resin composition to a substrate and drying it to volatilize the solvent. Subsequently, exposure and post-exposure baking steps are performed as necessary, followed by curing at a temperature of 150°C to 350°C. This heat treatment is performed by selecting a certain temperature and gradually increasing the temperature, or by selecting a certain temperature range and 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. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to ensure sufficient curing. There are no particular limitations on the upper limit of the curing conditions, but from the perspective of suppressing film shrinkage and stress, 280°C or lower is preferred, 250°C or lower is more preferred, and 230°C or lower is even more preferred.

[0138] When the cured film is patterned, the patterning may be carried out by a known method including a resin composition coating step, a drying step, an exposure step, a development step, a post-exposure baking step, a heat curing step, and the like.

[0139] The electronic component of the present invention has the cured film of the present invention.

[0140] A cured film formed from the photosensitive resin composition of the present invention can be used as an insulating film or a protective film that constitutes an electronic component.

[0141] Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.

[0142] Specific examples of the cured film in electronic components that can be suitably used include a passivation film for a semiconductor, a surface protection film for a semiconductor element, a TFT (Thin Film Transistor), etc., an interlayer insulating film such as an interlayer insulating film between rewirings in multilayer wiring for high-density packaging of 2 to 10 layers, an insulating film for a touch panel display, a protective film, and an insulating layer for an organic electroluminescent device, but the film is not limited thereto and can have various structures.

[0143] The substrate surface on which the cured film is formed can be appropriately selected depending on the application and process, and examples thereof include silicon, ceramics, glass, metal, and epoxy resin, and a plurality of these may be arranged on the same surface.

[0144] The antenna element using the cured film of the present invention will be described. The antenna element of the present invention comprises at least one or more antenna wirings and the cured film of the present invention, wherein the antenna wirings include one or more antennas selected from the group consisting of meandering loop antennas, coiled loop antennas, meandering monopole antennas, meandering dipole antennas, and planar antennas, and the area occupied by each antenna portion of the antenna wiring is 1000 mm ２ The cured film is an insulating film that insulates between the ground and the antenna wiring, and is an antenna element.

[0145] FIG. 1 is a schematic diagram of a coplanar-feed microstrip antenna, a type of planar antenna. 1a shows a cross-sectional view, and 1b shows a top view. First, the formation method will be described. The photosensitive resin composition of the present invention is applied to copper foil, pre-baked, exposed to light, and then laminated with copper foil and thermally cured to form a cured film having copper foil on both sides. After that, patterning is performed using a subtractive method, resulting in an antenna element having an antenna pattern of copper wiring for a microstrip line (MSL) as shown in FIG. 1.

[0146] Next, the antenna pattern in FIG. 1 will be described. In FIG. 1a, 15 denotes the ground (entire surface), and 16 denotes the insulating film that serves as the antenna substrate. The upper layers, 11 to 13, denote the cross-section of the antenna wiring obtained by the patterning. The ground wiring thickness J and the antenna wiring thickness K can be set to any thickness depending on the impedance design, but are typically 2 to 20 μm. In FIG. 1b, 11 denotes the antenna portion, 12 denotes a matching circuit, 13 denotes an MSL feed line, and 14 denotes a feed point. To match the impedance between the antenna portion 11 and the feed line 13, the length M of the matching circuit 12 is 1 / 4 λr (λr = (wavelength of transmitted radio wave) / (dielectric constant of insulating material) 1 / 2). The width W and length L of the antenna portion 11 are designed to be 1 / 2 λr. The antenna portion length L may be 1 / 2 λr or less depending on the impedance design. The cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, making it possible to provide a highly efficient and high-gain antenna element. In addition, due to these characteristics, the antenna element using the insulating film of the present invention is suitable as a high frequency antenna, and the area of ​​the antenna part (= L × W) is 1000 mm ２ By making the dimensions as follows, a small antenna element can be formed. In this way, a high-efficiency, high-gain, small-sized antenna element for high frequencies can be obtained.

[0147] Next, a semiconductor package including a semiconductor element such as an IC chip, a rewiring layer, a sealing resin, and an antenna wiring will be described. The semiconductor package of the present invention includes at least a semiconductor element, a rewiring layer, a sealing resin, and an antenna wiring, and the antenna wiring includes at least one antenna selected from the group consisting of a meandering loop antenna, a coiled loop antenna, a meandering monopole antenna, a meandering dipole antenna, and a microstrip antenna, and the area occupied by each antenna portion of the antenna wiring is 1000 mm ２ The semiconductor package is as follows: the insulating layer of the rewiring layer and / or the sealing resin includes the cured film of the present invention, and the sealing resin is located between the ground and the antenna wiring.

[0148] FIG. 2 is a schematic cross-sectional view of a semiconductor package including an IC chip (semiconductor element), rewiring, encapsulating resin, and an antenna element. A rewiring layer (two copper layers, three insulating layers) is formed on electrode pads 202 of an IC chip 201. The rewiring layer (copper wiring 209 and insulating film 210) is made of copper wiring 209 and an insulating film 210 formed using the cured film of the present invention. A barrier metal 211 and a solder bump 212 are formed on the pads of the rewiring layer (copper wiring 209 and insulating film 210). A first encapsulating resin 208 made of the cured film of the present invention is formed to encapsulate the IC chip, and a copper wiring 209 serving as an antenna ground is formed on top of the first encapsulating resin 208. A first via wiring 207 is formed through a via hole in the first encapsulating resin 208, connecting a ground 206 to the rewiring layer (copper wiring 209 and insulating film 210). A second encapsulating resin 205 made of the cured film of the present invention is formed on the first encapsulating resin 208 and the ground wiring 206, and a planar antenna wiring 204 is formed on top of the second encapsulating resin 205. A second via wiring 203 is formed connecting the planar antenna wiring 204 and the rewiring layer (copper wiring 209 and insulating film 210) through via holes formed in the first sealing resin 208 and the second sealing resin 205. The thickness of each insulating film 210 is preferably 10 to 20 μm, and the first sealing resin and the second sealing resin are preferably 50 to 200 μm and 100 to 400 μm, respectively. Because the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, a semiconductor package equipped with the resulting antenna element has high efficiency, high gain, and small transmission loss within the package.

[0149] That is, the electronic component of the present invention is an electronic component including at least one or more antenna wirings and an antenna element having the cured film of the present invention, wherein the antenna wirings include one or more antennas selected from the group consisting of meandering loop antennas, coiled loop antennas, meandering monopole antennas, meandering dipole antennas, and planar antennas, and the area occupied by each antenna portion of the antenna wiring is 1000 mm ２ The cured film is preferably an insulating film that insulates between the ground and the antenna wiring.

[0150] Furthermore, the electronic component of the present invention is an electronic component including a semiconductor package having at least a semiconductor element, a rewiring layer, a sealing resin, and an antenna wiring, and it is preferable that the insulating layer of the rewiring layer and / or the sealing resin includes the cured film of the present invention, and that the sealing resin also functions as an insulating film that insulates between the ground and the antenna wiring.

[0151] Furthermore, the electronic component of the present invention is an electronic component comprising an antenna element obtained by laminating an antenna wiring and the cured film of the present invention, and it is preferable that the height of the antenna wiring is 50 to 200 μm and the thickness of the cured film is 80 to 300 μm. By laminating the antenna wiring and the cured film and setting the height of the antenna wiring and the thickness of the cured film within the above ranges, a compact device can be made capable of transmitting and receiving signals over a wide range, and since the cured film of the present invention has a low dielectric constant and a low dielectric loss tangent, it is possible to provide an antenna element with high efficiency and high gain.

[0152] The compound of the present invention is a compound represented by formula (1) or a compound represented by formula (2).

[0153]

[0154] In formula (1), W １ and W ２ each independently represents a group represented by formula (3) or formula (4). In formula (1), a, b, c, and d each independently represent natural numbers satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0155]

[0156] In formula (2), W ３ and W ４ each independently represents a group represented by formula (3) or formula (4). In formula (2), e, f, g, and h each independently represent natural numbers satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0157]

[0158] In formula (3) and formula (4), X and Y represent —NH—.１ represents a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. ２ represents a single bond or a divalent organic group having 1 to 5 carbon atoms. i represents an integer of 1 to 5. * represents a bonding point.

[0159] The compounds of the present invention are capable of crosslinking by radical polymerization, and can be easily cured by combining them with a photo- or thermal radical generator. The resulting cured films have low dielectric constants and low dielectric loss tangents. They also have high solubility in organic solvents and excellent compatibility with many resins. Therefore, they can impart low dielectric properties to a variety of resins. While the reason for these properties is unclear, it is believed to be due to the presence of both low-polarity and high-polarity moieties within the molecule.

[0160] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods used in each example and comparative example will be described. For the evaluation, a photosensitive resin composition (hereinafter referred to as "varnish") before curing was used, which had been previously filtered through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore size of 1 μm.

[0161] (1) Pattern Processability The varnish was spin-coated onto a silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then pre-baked for 3 minutes at 100°C using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a pre-baked film with a thickness of 11 μm. The obtained pre-baked film was irradiated with 500 mJ / cm2 of light by contact using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) and an ultra-high pressure mercury lamp as a light source (mixture of g, h, and i lines). ２ It was exposed.

[0162] Thereafter, the sample was baked at 120°C for 1 minute after exposure and developed using a MARK-7 coating and developing apparatus. When developing with an organic solvent, puddle development was performed using a developer appropriate for the material being evaluated, followed by rinsing with a similarly appropriate rinse solution. The developer and rinse solutions used are shown in Table 4. When the photosensitive resin composition was soluble in an alkaline aqueous solution, development was performed with a 2.38% by mass aqueous solution of tetramethylammonium (TMAH), followed by rinsing with pure water.

[0163] Regarding the development time, the start time of development for each prebaked film was set to 0 seconds, and the time it took for the prebaked film to completely dissolve in the developer was measured between 0 and 90 seconds. If the prebaked film completely dissolved between 0 and 90 seconds, the development time was double that time. On the other hand, if the prebaked film did not completely dissolve within 90 seconds from the start of development, the development time was set to 3 minutes. The rinse time was 30 seconds for all cases. After development, the patterned area was observed, and developability was evaluated as follows: A: no residue remained in the 30 μm 1:1 line and space spaces; B: residue was observed; and C: the film did not dissolve in the developer and remained.

[0164] After development, the film thickness was measured, and the remaining film ratio was measured by dividing the film thickness after development of the exposed area by the prebaked film thickness, assuming the prebaked film thickness to be 100. Sensitivity was evaluated by rating a remaining film ratio of 80% or more as A, 50% or more but less than 80% as B, and less than 50% as C. The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., with a refractive index of 1.629. The same applies to film thicknesses described below.

[0165] (2) Measurement of dielectric constant and dielectric loss tangent The varnish was applied to a 6-inch silicon wafer by spin coating using a Mark-7 coating and developing apparatus so that the film thickness after pre-baking at 120°C for 3 minutes would be 11 μm, and then the entire surface was coated with PLA at 300 mJ / cm ２The sample was exposed to light, and then heated to 220°C at a rate of 3.5°C / min using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, and then heat-treated for 1 hour at each temperature. When the temperature reached 50°C or less, the silicon wafer was removed and immersed in 45% by weight hydrofluoric acid for 5 minutes to peel off the cured resin composition film from the wafer. This film was cut into strips 3 cm wide and 10 cm long, and the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using a perturbation cavity resonator method in accordance with ASTM D2520 at room temperature of 23.0°C and humidity of 45.0% RH. The dielectric properties were evaluated on a 5-point scale as shown in Table 1 below.

[0166]

[0167] (3) Measurement of Glass Transition Point A free-standing cured film was prepared in the same manner as in "(2) Measurement of Dielectric Constant and Dielectric Dissipation Factor" above. The cured film obtained by this method was cut into 3.0 cm x 1.5 cm pieces using a single-edged blade. The cured film was measured using a thermomechanical analyzer (Seiko Instruments, TMA / SS6100) under a nitrogen gas flow of 80 mL / min, with the temperature increased from 25°C to 400°C at a rate of 10°C / min (Measurement Method (I)). For cured films that could not be obtained as free-standing films, the cured film (a) was scraped off and measured using a differential scanning calorimeter (Shimadzu Corporation, DSC-50) under a nitrogen atmosphere, with the temperature increased from 25°C to 400°C at a rate of 10°C / min (Measurement Method (II)). Evaluation criteria were as follows: 4-point scale. A higher glass transition point indicates a higher heat resistance of the cured film. A: The glass transition point is 200°C or higher. B: The glass transition point is 170°C or higher and lower than 200°C. C: The glass transition point is 140°C or higher and lower than 170°C. D: The glass transition point is lower than 140°C.

[0168] (4) Measurement of elongation at break of cured film after curing A free-standing cured film was prepared in the same manner as in "(2) Measurement of dielectric constant and dielectric dissipation factor" above, and this film was cut into strips 1.5 cm wide and 9 cm long. Using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the film was stretched at a room temperature of 23.0°C and a humidity of 45.0% RH at a pulling rate of 50 mm / min (chuck spacing = 2 cm) to measure the elongation at break (%). Measurements were made on 10 strips per specimen, and the average of the top five highest numerical values ​​was calculated from the results.

[0169] Abbreviations for compounds used in the synthesis examples and examples are as follows: Priamine 1075: dimer diamine compound (trade name, manufactured by Croda Japan Co., Ltd.) (average amine value: 205) Karenz AOI: 2-acryloyloxyethyl isocyanate (trade name, manufactured by Showa Denko K.K.) Karenz BEI: 1,1-(bisacryloyloxymethyl)ethyl isocyanate (trade name, manufactured by Showa Denko K.K.) Polyflow 77: acrylic surfactant (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) Methylsilicate 51: silicate oligomer (trade name, manufactured by Colcoat Co., Ltd.) SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BFE: 1,2-bis(4-formylphenyl)ethane CP: cyclopentanone CYCLOTENE 4026-46: Benzocyclobutene solution (trade name, manufactured by Dow Chemical Co.) DCP-A: Dicyclopentadiene dimethacrylate (trade name, manufactured by Kyoeisha Chemical Co.) DFA: Dimethylformamide dimethyl acetal EL: Ethyl lactate HEMA: 2-hydroxyethyl methacrylate HA: 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane H ２O: Ultrapure water IPA: 2-propanol IRGANOX3114: Hindered phenol antioxidant (trade name, manufactured by BASF Corporation) GBL: γ-butyrolactone KC Cleaner NX: C10-12 isoparaffin (trade name, manufactured by Keiyo Chemical Co., Ltd.) MEHC-7851SS: Phenolic resin (trade name, manufactured by Meiwa Kasei Co., Ltd.) MOM: 4-[1,1-bis[4-hydroxy-3,5-bis(methoxymethyl)phenyl]ethyl]-2,6-bis(methoxymethyl)phenol NA: 5-norbornene-2,3-dicarboxylic anhydride NCI-831: Photopolymerization initiator (trade name, manufactured by ADEKA Corporation) NMP: N-methyl-2-pyrrolidone ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride OXT-121: Oxetane compound (trade name, manufactured by Toagosei Co., Ltd.) PGMEA: Propylene glycol methyl ether acetate TMAH: Tetramethylammonium aqueous solution VG-3101: Monomeric triphenylmethane epoxy resin (trade name, manufactured by Printec Co., Ltd.) U-847: Acrylic monomer having a urethane group and the following structure (trade name, manufactured by Designer Molecules Inc.)

[0170]

[0171] XIRAN2000: styrene-maleic anhydride copolymer resin (trade name, manufactured by Tomoe Engineering Co., Ltd.) APL6015T: cycloolefin polymer (trade name, manufactured by Mitsui Chemicals, Inc.) BMI-689: monomer having a maleimide group and the following structure (trade name, manufactured by Designer Molecules Inc.)

[0172]

[0173] Example 1: Synthesis of Multifunctional Monomer (M-1) Under a dry nitrogen stream, 28.22 g (0.20 mol) of Karenz AOI and 28.22 g of toluene were placed in a three-neck flask and stirred. A solution of 53.50 g (0.10 mol) of Priamine 1075 dissolved in 53.50 g of toluene was then added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours, and the toluene was then removed using an evaporator to obtain multifunctional monomer (M-1). A nuclear magnetic resonance spectrometer (JNM-ECZ400R, manufactured by JEOL Ltd.) was used to identify the structure of the resulting multifunctional monomer. The results are shown below. １ H-NMR (DMSO): 6.4 (d, 2H), 6.0-6.2 (m, 6H), 5.8 (d, 2H), 4.3 (m, 4H), 3.4 (m, 4H), 3.1 (m, 4H), 1.2-1.5 (m, 60H), 0.9 (t, 6H).

[0174]

[0175] Example 2 Synthesis of Polyfunctional Monomer (M-2) Polyfunctional monomer (M-2) was obtained in the same manner as in Synthesis Example 1, except that 28.22 g (0.20 mol) of Karenz AOI in Synthesis Example 1 was replaced with 47.84 g (0.20 mol) of Karenz BEI. The results of NMR used to identify the structure of the obtained polyfunctional monomer are shown below. １ H-NMR (DMSO): 6.4-6.6 (m, 6H), 6.0-6.2 (m, 6H), 5.8 (d, 4H), 4.8 (s, 8H), 3.1 (m, 4H), 1.6 (s, 6H), 1.2-1.5 (m, 60H), 0.9 (t, 6H).

[0176]

[0177] [Synthesis Example 1 Synthesis of Polyimide (P-1)] Under a dry nitrogen stream, 31.13 g (0.085 mol) of BAHF, 1.24 g (0.0050 mol) of SiDA, 2.18 g (0.020 mol) of MAP as an end-capping agent, and 150.00 g of NMP were weighed and dissolved in a three-necked flask. To this, a solution of 31.02 g (0.10 mol; 100 mol% based on all structural units derived from carboxylic acids and derivatives thereof) of ODPA dissolved in 50.00 g of NMP was added, stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After completion of the reaction, the reaction solution was poured into 3 L of water, and the precipitated solid was obtained by filtration. The resulting solid was washed with water three times and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (P-1).

[0178] [Synthesis Example 2: Synthesis of Polyamide (P-2)] In a 500 mL round-bottom flask filled with toluene and equipped with a Dean-Stark water separator and a condenser, 19.98 g (0.095 mol; 95.0 mol% relative to all structural units derived from amines and their derivatives) of bis(4-aminocyclohexyl)methane, 1.24 g (0.0050 mol; 5.0 mol% relative to all structural units derived from amines and their derivatives), and 70.00 g of NMP were weighed and dissolved. A solution of 19.06 g (0.080 mol; 66.7 mol% relative to all structural units derived from carboxylic acids and their derivatives) of BFE dissolved in 20.00 g of NMP was added thereto, and the mixture was stirred at 20°C for 1 hour, and then at 50°C for 2 hours. Next, a solution of 6.57 g (0.040 mol; 33.3 mol% based on all structural units derived from carboxylic acids and their derivatives) of NA dissolved in 10 g of NMP as an end-capping agent was added, and the mixture was stirred at 50°C for 2 hours. Thereafter, the mixture was stirred at 100°C for 2 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was poured into 3 L of water, and the deposited solid precipitate was obtained by filtration. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80°C for 24 hours to obtain polyamide (P-2).

[0179] Synthesis Example 3: Synthesis of Polyurea (P-3) Under a dry nitrogen stream, a solution prepared by dissolving 6.00 g (0.020 mol) of 4,4'-diphenylmethane diisocyanate in 30 g of NMP was charged into a three-necked flask. While stirring the solution in the flask, a solution prepared by dissolving 3.52 g (0.013 mol) of 2-(3',5'-diaminobenzyloxy)ethyl methacrylate in 20 g of NMP was added to the solution, and the mixture was stirred at 50°C for 4 hours. After completion of the reaction, the reaction solution was charged into 500 g of methanol, and the resulting solid precipitate was collected by filtration. The resulting solid was dried in a vacuum dryer for 24 hours to obtain Polyurea (P-3).

[0180] Synthesis Example 4: Synthesis of Polyester Resin Solution (P-4) 148 g of 1,1-bis(4-(2,3-epoxypropyloxy)phenyl)-3-phenylindane, 47 g of acrylic acid, 1 g of tetrabutylammonium acetate (TBAA), 2.0 g of tert-butylcatechol, and 244 g of PGMEA were charged and stirred at 120°C for 5 hours. After cooling to room temperature, 30 g of biphenyltetracarboxylic dianhydride and 1 g of TBAA were added, and the mixture was stirred at 110°C for 3 hours. After cooling to room temperature, 15 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120°C for 5 hours. After completion of the reaction, 500 g of PGMEA was added, and the reaction solution was subjected to liquid separation and extraction with a 1 N aqueous formic acid solution to remove the addition catalyst. The mixture was dried over magnesium sulfate and then concentrated using a rotary evaporator to a solids concentration of 40 wt %, yielding a polyester resin solution (P-4).

[0181] Synthesis Example 5: Synthesis of Polysiloxane Solution (P-5) Under a dry nitrogen stream, a 500 ml three-neck flask was charged with 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5.88 g (corresponding to 0.05 moles of Si atom) of methyl silicate 51, and 155.04 g of propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMEA), and an aqueous phosphoric acid solution prepared by dissolving 0.515 g of phosphoric acid (0.30 parts by mass based on the charged monomers) in 54.45 g of water was added over 10 minutes with stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the solution was then heated and stirred for 2 hours (internal temperature: 100°C), yielding a polysiloxane solution (P-5).

[0182] Synthesis Example 6: Synthesis of Acrylic Resin Solution (P-6) A 500 ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA. Then, 23.0 g of methacrylic acid, 31.5 g of benzyl methacrylate, and 32.8 g of tricyclo[5.2.1.02,6]decan-8-yl methacrylate were charged and stirred at room temperature for a while. The atmosphere in the flask was thoroughly purged with nitrogen by bubbling, and then heated and stirred at 70 °C for 5 hours. Next, 12.7 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 °C for 4 hours. After stirring, PGMEA was added so that the solids concentration was 40 wt %, and an acrylic resin solution (P-6) was obtained.

[0183] Synthesis Example 7: Synthesis of Polyimide Precursor (P-7) Under a dry nitrogen stream, 31.02 g (0.10 mol) of ODPA was placed in a 500 ml separable flask, 26.03 g (0.20 mol) of HEMA, and 123.0 ml of NMP were placed in a three-neck flask, and 22.26 g (0.22 mol) of triethylamine was added to the mixture with stirring at room temperature to obtain a reaction mixture. After the end of the heat generation due to the reaction, the mixture was allowed to cool to room temperature and left for 16 hours. Next, the temperature was raised to 40°C, and 76.7 g (0.2 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate was added to the reaction mixture, followed by stirring for 30 minutes. After further stirring at room temperature for 2 hours, 17.88 g of bis(4-aminocyclohexyl)methane (0.085 mol; 77.3 mol% relative to all structural units derived from amines and their derivatives), 1.24 g of SiDA (0.0050 mol; 4.5 mol% relative to all structural units derived from amines and their derivatives), 2.18 g of MAP (0.020 mol; 18.2 mol% relative to all structural units derived from amines and their derivatives) as an end-capping agent, and 77.00 g of NMP were added and stirred for 1 hour to obtain a reaction solution. The resulting reaction solution was allowed to cool to room temperature and added to 3 L of water to produce a precipitate consisting of a crude polymer. This precipitate was collected by filtration, washed three times with water, then washed twice with 500 mL of isopropyl alcohol, and vacuum dried to obtain a powdered polyimide precursor (P-7).

[0184] Synthesis Example 8: Synthesis of Polyimide Precursor (P-8) Polyimide precursor (P-8) was obtained in the same manner as in Synthesis Example 5, except that 26.03 g (0.20 mol) of HEMA was replaced with 53.70 g (0.20 mol) of oleyl alcohol.

[0185] Synthesis Example 9: Synthesis of Polyimide Precursor (P-9) Under a dry nitrogen stream, 51.4 g (0.085 mol) of HA, 1.24 g (0.005 mol) of SiDA, and 2.18 g (0.020 mol) of MAP as an end-capping agent were dissolved in 200 g of NMP. 31.0 g (0.10 mol) of ODPA was added thereto, and the mixture was stirred at 40°C for 2 hours. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of DFA with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, stirring was continued for 2 hours at 40°C. After stirring was completed, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. The mixture was further washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain polyimide precursor (P-9).

[0186] Synthesis Example 10: Synthesis of Polybenzoxazole (P-10) In a 500 mL round-bottom flask filled with toluene and equipped with a Dean-Stark water separator and a condenser, 34.79 g (0.095 mol; 95.0 mol% relative to all structural units derived from amines and their derivatives) of BAHF, 1.24 g (0.0050 mol; 5.0 mol% relative to all structural units derived from amines and their derivatives) of SiDA, and 75.00 g of NMP were weighed and dissolved. To this, a solution of 19.06 g (0.080 mol; 66.7 mol% relative to all structural units derived from carboxylic acids and their derivatives) of BFE and 6.57 g (0.040 mol; 33.3 mol% relative to all structural units derived from carboxylic acids and their derivatives) of NA as an end-capping agent was added, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 1 hour. The mixture was then heated and stirred at 200°C or higher for 10 hours under a nitrogen atmosphere to carry out a dehydration reaction. After completion of the reaction, the reaction solution was poured into 3 L of water, and the resulting solid precipitate was collected by filtration. The resulting solid was washed three times with water and then dried in a vacuum dryer at 80°C for 24 hours to obtain polybenzoxazole (P-10).

[0187] Synthesis Example 11 Synthesis of Polybenzoxazole Precursor (P-11) In a 500 mL round-bottom flask filled with toluene and equipped with a Dean-Stark water separator and a condenser, 34.79 g (0.095 mol; 95.0 mol% relative to all structural units derived from amines and their derivatives) of BAHF, 1.24 g (0.0050 mol; 5.0 mol% relative to all structural units derived from amines and their derivatives) of SiDA, and 70.00 g of NMP were weighed and dissolved. To this, a solution of 19.06 g (0.080 mol; 66.7 mol% relative to all structural units derived from carboxylic acids and their derivatives) of BFE dissolved in 20.00 g of NMP was added, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 2 hours. Next, a solution of 6.57 g (0.040 mol; 33.3 mol% based on all structural units derived from carboxylic acids and their derivatives) of NA dissolved in 10 g of NMP as an end-capping agent was added, and the mixture was stirred at 50°C for 2 hours. Thereafter, the mixture was stirred at 100°C for 2 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was poured into 3 L of water, and the deposited solid precipitate was obtained by filtration. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polybenzoxazole precursor (P-11).

[0188] Synthesis Example 12: Synthesis of Polyimide (P-12) Under a dry nitrogen stream, 27.47 g (0.075 mol) of BAHF, 1.24 g (0.0050 mol) of SiDA, 5.35 g (0.010 mol) of Priamine 1075 as an end-capping agent, 2.18 g (0.020 mol) of MAP, and 150.00 g of NMP were weighed and dissolved in a three-neck flask. To this was added a solution of 31.02 g (0.10 mol) of ODPA dissolved in 50.00 g of NMP, and the mixture was stirred at 20°C for 1 hour, and then at 50°C for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotropically distilling water with xylene. After completion of the reaction, the reaction solution was poured into 3 L of water, and the precipitated solid was collected by filtration. The resulting solid was washed with water three times and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (P-12).

[0189] Example 3: Under yellow light, 10.00 g of BMI-689, 10.00 g of polyimide resin (P-1), 0.50 g of NCI-831, 0.10 g of IRGANOX3114, and 0.30 g of 3-trimethoxysilylphthalamic acid were dissolved in 20.00 g of NMP, and 0.10 g of a 1% by mass EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured using the evaluation methods described above, including pattern processability, dielectric constant, dielectric dissipation factor, glass transition temperature, and elongation at break.

[0190] Example 4 The same procedure as in Example 3 was carried out, except that BMI-689 was replaced with U-847.

[0191] [Example 5] Under yellow light, 10.00 g of M-1, 10.00 g of polyamide resin (P-2), 0.50 g of NCI-831, 0.10 g of IRGANOX3114, and 0.30 g of 3-trimethoxysilylphthalamic acid were dissolved in 20.00 g of NMP, and 0.10 g of a 1% by mass EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured in the same manner as in Example 3.

[0192] Example 6: The same procedure as in Example 5 was carried out except that P-2 was replaced with P-3.

[0193] Example 7 The same procedure as in Example 5 was carried out, except that P-2 was replaced with P-4.

[0194] Example 8 The same procedure as in Example 5 was carried out, except that P-2 was replaced with P-5.

[0195] Example 9 The same procedure as in Example 5 was carried out, except that P-2 was replaced with P-6.

[0196] Example 10 The procedure of Example 5 was repeated except that P-2 was replaced with MEHC-7851SS.

[0197] Example 11 The same procedure as in Example 5 was carried out, except that P-2 was replaced with CYCLOTENE 4026-46.

[0198] [Example 12] Under yellow light, 10.00 g of M-1, 10.00 g of XIRAN2000, 0.50 g of NCI-831, 0.10 g of IRGANOX3114, and 0.30 g of 3-trimethoxysilylphthalamic acid were dissolved in 20.00 g of toluene, and 0.10 g of a 1% by mass EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured in the same manner as in Example 3.

[0199] Example 13 The same procedure as in Example 12 was carried out, except that XIRAN2000 was replaced with APL6015T.

[0200] Example 14 The procedure of Example 5 was repeated except that P-2 was replaced with P-1.

[0201] Example 15 The procedure of Example 14 was repeated except that M-1 was replaced with M-2.

[0202] Example 16 The same procedure as in Example 5 was carried out, except that P-2 was replaced with P-7.

[0203] Example 17 The same procedure as in Example 5 was carried out, except that P-2 was replaced with P-8.

[0204] Example 18 The procedure of Example 5 was repeated except that P-2 was replaced with P-9.

[0205] Example 19 The same procedure as in Example 5 was carried out, except that P-2 was replaced with P-10.

[0206] Example 20 The procedure of Example 5 was repeated except that P-2 was replaced with P-11.

[0207] Example 21 The procedure of Example 5 was repeated except that P-2 was replaced with P-12.

[0208] Example 22 The same procedure as in Example 5 was repeated, except that 10.00 g of P-2 was replaced with 8.00 g of P-12 and 2.00 g of MEHC-7851SS.

[0209] Example 23 The same procedure as in Example 22 was carried out, except that 2.00 g of VG-3101 was added to the mixture.

[0210] Example 24 The same procedure as in Example 22 was carried out, except that 2.00 g of OXT-121 was added to the mixture.

[0211] Example 25 The same procedure as in Example 22 was carried out, except that 2.00 g of MOM was added to the mixture.

[0212] [Comparative Example 1] Under yellow light, 10.00 g of P-1, 10.00 g of DCP-A, 0.50 g of NCI-831, 0.10 g of IRGANOX3114, 0.30 g of 3-trimethoxysilylphthalamic acid, and 2.00 g of MOM were dissolved in 27.00 g of NMP, and 0.10 g of a 1% by mass EL solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured using the evaluation methods described above, including pattern processability, dielectric constant, dielectric dissipation factor, glass transition temperature, and elongation at break.

[0213]

[0214]

[0215]

[0216] 1a Cross-sectional view 1b Top view 11 Antenna section 12 Matching circuit 13 MSL feed line 14 Feed point 15 Ground 16 Insulating film J Ground wiring thickness K Antenna wiring thickness L Antenna section length M Matching circuit length W Antenna section width 201 IC chip 202 Electrode pad 203 Second via wiring 204 Planar antenna wiring 205 Second sealing resin 206 Ground 207 First via wiring 208 First sealing resin 209 Copper wiring 210 Insulating film 211 Barrier metal 212 Solder bump

Claims

1. A photosensitive resin composition comprising (A) a polyfunctional monomer, (B) a binder resin, and (C) a photopolymerization initiator, wherein the (A) polyfunctional monomer comprises a compound represented by formula (1) and / or a compound represented by formula (2), in which at least one of W 1 and W 2 and at least one of W 3 and W 4 in formula (1) and formula (2) are groups represented by formula (3), formula (4), formula (5), or formula (6), and the (B) binder resin comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, and maleic acid resin. 【Chemistry 1】 (In formula (1), W １ and W. ２ each independently represents a monovalent organic group having 2 to 25 carbon atoms and a carbon-carbon double bond. In formula (1), a, b, c, and d each independently represent natural numbers satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. 【Chemistry 2】 (In formula (2), W ３ and W. ４ each independently represents a monovalent organic group having 2 to 25 carbon atoms and a carbon-carbon double bond. In formula (2), e, f, g, and h each independently represent natural numbers satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. 【Chemistry 3】 【Chemistry 4】 (In formulas (3), (4), (5) and (6), X and Y each independently represent -NH-, -O-, -CH2- or -S-. R1 represents a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. R2 represents a single bond or a divalent organic group having 1 to 5 carbon atoms. i represents an integer of 1 to 5. * represents a bonding point.)

2. A photosensitive resin composition comprising (A) a polyfunctional monomer, (B) a binder resin, and (C) a photopolymerization initiator, wherein the (A) polyfunctional monomer comprises a compound represented by formula (1) and / or a compound represented by formula (2), wherein in formulas (1) and (2), at least one of W 1 and W 2 and at least one of W 3 and W 4 are groups represented by formula (3) or formula (4), wherein in formulas (3) and (4), X and Y are -NH-, and the (B) binder resin comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, copolymers thereof, polyurea, polyester, polysiloxane, acrylic resin, phenolic resin, benzocyclobutene resin, maleic acid resin, and cycloolefin polymer. 【Chemistry 5】 (In formula (1), W 1 and W 2 each independently represent a monovalent organic group having 2 to 25 carbon atoms and a carbon-carbon double bond. In formula (1), a, b, c, and d each independently represent natural numbers satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed lines represent a carbon-carbon single bond or a carbon-carbon double bond.) 【Chemistry 6】 (In formula (2), W 3 and W 4 each independently represent a monovalent organic group having 2 to 25 carbon atoms and a carbon-carbon double bond. In formula (2), e, f, g, and h each independently represent natural numbers satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.) 【Chemistry 7】 (In formula (3) and formula (4), X and Y represent --NH--. R 1 represents a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. R 2 represents a single bond or a divalent organic group having 1 to 5 carbon atoms. i represents an integer of 1 to 5. * represents a bonding point.)

3. In the formula (1) and the formula (2), W １ and W. ２ At least one of the above and W ３ and W. ４ At least one of the groups represented by formula (3) or formula (4) is 2. The photosensitive resin composition according to claim 1, wherein in the formula (3) and the formula (4), X and Y are -NH-.

4. In the formula (1) and the formula (2), W １ and W. ２ At least one of the above and W ３ and W. ４ The photosensitive resin composition according to claim 1 or 2, wherein at least one of the following is a group represented by formula (8), formula (9), formula (10) or formula (11): 【Chemistry 8】 【Chemistry 9】 (* indicates the attachment point.)

5. 2. The photosensitive resin composition according to claim 1, wherein the binder resin (B) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, each of which is obtained by polymerizing a dimer acid derivative as a monomer.

6. The photosensitive resin composition according to claim 1 or 5, wherein the binder resin (B) further contains a phenolic resin having a biphenyl structure.

7. The photosensitive resin composition according to any one of claims 1 to 3 and 5, further comprising a crosslinking agent (D), the crosslinking agent (D) comprising one or more compounds selected from the group consisting of epoxy compounds, oxetane compounds, and methylol compounds.

8. The photosensitive resin composition according to claim 7, wherein the (D) crosslinking agent contains a methylol compound.

9. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 3 and 5.

10. An electronic component having the cured film according to claim 9.

11. An antenna element comprising at least one antenna wiring and the cured film according to claim 9, wherein the antenna wiring includes at least one antenna selected from the group consisting of a meandering loop antenna, a coiled loop antenna, a meandering monopole antenna, a meandering dipole antenna, and a planar antenna, and the area occupied by each antenna part in the antenna wiring is 1000 mm2 or less. ２ The antenna element according to claim 1, wherein the cured film is an insulating film that provides insulation between the ground and the antenna wiring.

12. A semiconductor package comprising at least a semiconductor element, a rewiring layer, a sealing resin, and an antenna wiring, the antenna wiring including at least one antenna selected from the group consisting of a meandering loop antenna, a coiled loop antenna, a meandering monopole antenna, a meandering dipole antenna, and a microstrip antenna, and the area occupied by each antenna portion in the antenna wiring is 1000 mm ２ 10. A semiconductor package comprising: an insulating layer of a redistribution layer and / or a sealing resin comprising the cured film according to claim 9; and a sealing resin disposed between a ground and an antenna wiring.

13. 11. The electronic component according to claim 10, comprising an antenna element obtained by laminating an antenna wiring and the cured film according to claim 9, wherein the height of the antenna wiring is 50 to 200 μm, and the thickness of the cured film is 80 to 300 μm.

14. A compound represented by formula (1) or a compound represented by formula (2): 【Chemistry 10】 (In formula (1), W １ and W. ２ each independently represents a group represented by formula (3) or formula (4). In formula (1), a, b, c, and d each independently represent a natural number satisfying a+b=6 to 17 and c+d=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. 【Chemistry 11】 (In formula (2), W ３ and W. ４ each independently represents a group represented by formula (3) or formula (4). In formula (2), e, f, g, and h each independently represent a natural number satisfying e+f=5 to 16 and g+h=8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. 【Chemistry 12】 (In formula (3) and formula (4), X and Y represent -NH-. R １ R represents a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. ２ represents a single bond or a divalent organic group having 1 to 5 carbon atoms. i represents an integer of 1 to 5. * represents a bonding point.

Images