Resin, photosensitive resin composition and cured products of same, and electronic component and display device each using said cured product

Abstract

The present invention addresses the problem of providing a resin which is advantageous in terms of dielectric constant, water absorbability, and heat resistance. In order to solve the problem, the present invention proposes a resin which has at least a repeating unit represented by formula (1) and a repeating unit represented by formula (2), wherein when all repeating units contained in the resin is taken as 100 mol%, the repeating unit represented by formula (1) is contained in an amount of not less than 30 mol% but less than 100 mol%. (In the formula, R1 represents a hydrogen atom or a methyl group.) (In the formula, X1 represents -O- or -NH-, and Y1 represents a monovalent organic group having 2 to 30 carbon atoms and having a carbon-carbon double bond or a carbon-carbon triple bond.)

Description

Resin, photosensitive resin composition, and cured product thereof, and electronic component and display device using said cured product

[0001] The present invention relates to a resin, a photosensitive resin composition, a cured product, an electronic component, and a display device.

[0002] Wiring that electrically connects elements and devices, and an interlayer insulating film that insulates them, are essential for electronic components and display devices. Various resins, such as acrylic resins and polyimide resins, are selected for this interlayer insulating film depending on the application, and properties such as insulation, adhesion, heat resistance, and processability are required. For example, Patent Document 1 exemplifies a semiconductor device using an alkali-developable photosensitive polyimide, and Patent Document 2 exemplifies a display device using a photosensitive acrylic resin. In recent years, with the trend toward finer wiring, higher signal frequencies, and improved display performance, interlayer insulating films are required to have higher characteristics than ever before. Specific examples include low dielectric constant, low dielectric loss tangent, low water absorption, heat resistance, and adhesion. Transparency may also be required for display devices.

[0003] JP 2020-66651 A International Publication No. 2014 / 050324

[0004] As electronic components and display devices become more sophisticated and functional, interlayer insulating films are required to have low dielectric constants, low water absorption, and high heat resistance. However, existing acrylic resins, for example, have high dielectric constants and low heat resistance. Furthermore, existing polyimide resins have high dielectric constants and water absorption, so there is a demand for materials with even lower dielectric constants, lower water absorption, and higher heat resistance.

[0005] Therefore, an object of the present invention is to provide a resin that is advantageous in terms of dielectric constant, water absorption, and heat resistance and that can cope with the increasing performance and functionality of such electronic parts and display devices.

[0006] In order to solve the above problems, the present invention has the following configuration: [1] A resin having at least a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein when all repeating units contained in the resin are taken as 100 mol %, the repeating unit represented by formula (1) accounts for 30 mol % or more but less than 100 mol %:

[0007]

[0008] (R １ represents a hydrogen atom or a methyl group.

[0009]

[0010] (X １ represents —O— or —NH—. １ represents a monovalent organic group having 2 to 30 carbon atoms and a carbon-carbon double bond or a carbon-carbon triple bond.) [2] X in the formula (2) １ is —NH—, and Y １ is a group represented by the following formula (3):

[0011]

[0012] (Ar represents a divalent aromatic ring having 6 to 18 carbon atoms. Y ２ represents a vinyl group or an ethynyl group. * represents X １ [3] The resin according to [1] or [2] above, having an acid value of 50 mgKOH / g or more and 200 mgKOH / g or less. [4] The resin according to any one of [1] to [3] above, further having a repeating unit represented by the following formula (4):

[0013]

[0014] (X ２ represents —O— or —NH—. １represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms and no carbon-carbon double or triple bond.) [5] A cured product obtained by curing the resin according to any one of [1] to [4] above. [6] A photosensitive resin composition containing the resin according to any one of [1] to [4] above and a photosensitizer, wherein at least one of the photosensitizers is a compound selected from the group consisting of a photoradical polymerization initiator, a photoacid generator, and a naphthoquinone diazide compound. [7] The photosensitive resin composition according to [6] above, further containing one or more resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, polysiloxane, and phenolic resin. [8] The photosensitive resin composition according to [6] or [7] above, further containing a crosslinking agent. [9] The photosensitive resin composition according to any one of [6] to [8] above, further containing a reaction inhibitor represented by formula (9).

[0015]

[0016] (R １８ and R １９ are each independently a hydrogen atom, a fluorine atom, or —CF ３ , -NO ２ or -NO, with the proviso that R １８ and R １９ At least one of the groups is a fluorine atom, —CF ３ , -NO ２ Or -NO. s represents 0 or 1.)

[10] A cured product obtained by curing the photosensitive resin composition according to any one of [6] to [9] above.

[11] An electronic part comprising the cured product according to [5] or

[10] above.

[12] A display device comprising the cured product according to [5] or

[10] above.

[0017] The resin of the present invention has a low dielectric constant, a low dielectric dissipation factor, low water absorption, alkali solubility, crosslinkability, and heat resistance, and can be used in applications requiring these properties. The photosensitive resin composition of the present invention is patternable by photolithography and can provide a cured product with a low dielectric constant, a low dielectric dissipation factor, low water absorption, and high heat resistance. By using the cured product of the present invention, it is possible to provide electronic components and display devices with low loss at high frequencies and low power consumption.

[0018] 3A and 3B are schematic diagrams of a planar antenna, which is an example of an electronic component of the present invention, in which FIG. 3A is a cross-sectional view and FIG. 3B is a top view.

[0019] The resin of the present invention contains a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) in at least one molecule, and when the total amount of all repeating units contained in the resin is taken as 100 mol %, the repeating unit represented by formula (1) accounts for 30 mol % or more but less than 100 mol % (hereinafter, this resin of the present invention may be referred to as "resin (A)"). From the viewpoints of reduced dielectric loss tangent and alkaline solubility, the repeating structural unit represented by formula (1) in the resin is preferably 40 mol % or more but less than 80 mol %, and more preferably 45 mol % or more but less than 60 mol %. The repeating structural unit represented by formula (2) in the resin preferably has a lower limit of 10 mol % or more, and even more preferably 40 mol % or more, and an upper limit of 70 mol % or less, even more preferably 60 mol % or less, and even more preferably 55 mol % or less. By ensuring that the content of the repeating unit represented by formula (1) is within this range, a low dielectric constant, a low dielectric loss tangent, and low water absorption can be achieved. Furthermore, by containing the repeating unit represented by formula (2), alkali solubility and crosslinkability can be imparted.

[0020]

[0021] (R １ represents a hydrogen atom or a methyl group.

[0022]

[0023] (X １represents —O— or —NH—. １ represents a monovalent organic group having 2 to 30 carbon atoms and a carbon-carbon double bond or a carbon-carbon triple bond. １ is preferably —NH—, since imidization proceeds by heat treatment and heat resistance can be improved.

[0024] Y １ is X １ Preferably, the Y has an organic group such as a linear aliphatic group, a cyclic aliphatic group, or an aromatic ring at the side thereof and a carbon-carbon double bond or a carbon-carbon triple bond at the terminal. Of the carbon-carbon double bonds and carbon-carbon triple bonds, the carbon-carbon double bond is preferred from the viewpoint of reactivity. １ The portion other than the carbon-carbon double bond or carbon-carbon triple bond contained in may contain multiple types of linear aliphatic groups, cyclic aliphatic groups, or aromatic rings via an ether group, a carbonyl group, an ester group, an amide group, etc. More specifically, the following structures can be mentioned (in each case, * represents X １ represents the point of attachment to a carbon-carbon double bond or a carbon-carbon triple bond.)

[0025]

[0026] Y １ is preferably a group represented by the following formula (3):

[0027]

[0028] (Ar represents a divalent aromatic ring having 6 to 18 carbon atoms. Y ２ represents a vinyl group (also called an ethenyl group) or an ethynyl group. * represents X １(Indicates the bonding point with the .) In the present invention, the acid value of resin (A) is preferably 50 mgKOH / g or more and 200 mgKOH / g or less. More preferably, it is 70 mgKOH / g or more and 150 mgKOH / g or less. When it is in this range, when it is used in a photosensitive resin composition, it becomes easier to achieve both patterning properties with an alkaline developer and properties of low dielectric constant, low dielectric tangent, and low water absorption. The acid value here refers to the weight of potassium hydroxide that reacts with 1 g of resin, and is expressed in mgKOH / g. The acid value can be determined by titrating 1 g of resin with an aqueous potassium hydroxide solution.

[0029] Next, a method for synthesizing resin (A) will be described. The repeating unit represented by formula (1) can be considered to be a repeating unit derived from styrene or α-methylstyrene (hereinafter, sometimes referred to as "styrenes"). The repeating unit represented by formula (2) can be considered to be a repeating unit derived from a maleic acid derivative. That is, resin (A) of the present invention can be obtained by a polymerization reaction between styrenes and maleic acid derivatives. The structure of formula (2) can be obtained by polymerizing a precursor that provides the repeating unit of formula (2). Alternatively, a polymer can be synthesized using either or both maleic acid and maleic anhydride (hereinafter, sometimes referred to as "maleic acids") as monomers, and then an alcohol compound or an amine compound can be reacted with the resulting polymer to obtain the repeating unit of formula (2). That is, resin (A) can be obtained by using a polymer obtained from styrenes and maleic acids as monomers as a precursor and reacting the precursor with an alcohol compound or an amine compound. When the precursor is an anhydride, an alcohol compound can be reacted using a tertiary amine or a quaternary ammonium compound as a catalyst to introduce an ester group. When the precursor is an anhydride, the amine compound can be reacted without a catalyst to introduce an amide group. When the precursor is a dicarboxylic acid, both the alcohol compound and the amine compound can be reacted using a known dehydration condensation agent.

[0030] The weight average molecular weight of the resin (A) is not particularly limited, but is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and even more preferably from 7,000 to 25,000. When the weight average molecular weight is within this range, heat resistance and processability are improved.

[0031] The precursor can be synthesized by any known method, including, for example, radical polymerization of styrenes and maleic acids. Azo compounds such as azobisisobutyronitrile or organic peroxides such as benzoyl peroxide are commonly used as catalysts for radical polymerization. Alternatively, commercially available styrene / maleic anhydride copolymers may be used as the precursor. Examples of commercially available copolymers include XIRAN-1000, XIRAN-2000, XIRAN-3000, XIRAN-4000, XIRAN-6000, and XIRAN-9000 (all manufactured by Polyscope).

[0032] The alcohol compound is not particularly limited as long as it is a compound having an alcoholic hydroxyl group and a carbon-carbon double bond or a carbon-carbon triple bond, and examples thereof 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, 2-hydroxy-3-cyclohexyloxypropyl (meth)acrylate, 2-(meth)acryloxyethyl-2-hydroxypropyl phthalate, and allyl alcohol. compounds having one carbon-carbon double bond and one alcoholic hydroxyl group, such as butenyl alcohol, pentenyl alcohol, and hexenyl alcohol; 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, and glycerin-1-allyloxy-2-methacrylate; Examples of the (meth)acrylate include compounds having two carbon-carbon double bonds and one alcoholic hydroxyl group, such as 2-methyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), and 2-((acryloyloxy)-2-(hydroxymethyl)butyl methacrylate. Here, the term "(meth)acrylate" refers to both methacrylate and acrylate. An example of an alcohol having a carbon-carbon triple bond is propargyl alcohol.

[0033] The amino compound is not particularly limited as long as it is a compound having a primary amino group or a secondary amino group and a carbon-carbon double bond or a carbon-carbon triple bond, and examples thereof include aliphatic amines such as allylamine, butenylamine, pentenylamine, hexenylamine, and propargylamine, and aromatic amines such as 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, 2-aminophenylacetylene, 3-aminophenylacetylene, 4-aminophenylacetylene, and 1-amino-4-vinylnaphthalene.

[0034] The resin (A) may further have a repeating unit represented by the following formula (4): By containing the repeating unit of formula (4), various functions can be imparted.

[0035]

[0036] (X ２ represents —O— or —NH—. １ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms and having no carbon-carbon double bond or carbon-carbon triple bond.) C(═O)—X in the formula (4) ２ -Z １ By appropriately selecting the structure of (A), various functions can be imparted to the resin (A). For example, a phenolic hydroxyl group or a carboxyl group can be selected to adjust alkali solubility, a long-chain aliphatic group can be selected to reduce the elastic modulus, an alkoxysilyl group, a sulfonyl group, a heterocycle-containing organic group, a sulfide group, or the like can be selected to impart adhesion, and an acid-dissociable functional group can be selected to impart positive photosensitivity.

[0037] Examples of methods for introducing the repeating unit of formula (4) include reacting a polymer obtained from styrenes and maleic acids as monomers with an alcohol compound, an amine compound, a vinyl ether compound, or the like that does not have a carbon-carbon double bond or a carbon-carbon triple bond. The method for reacting a polymer obtained from styrenes and maleic acids as monomers with an alcohol compound or an amine compound is the same as that described above for the method for introducing the repeating unit of formula (2). Examples of the reaction between a precursor and a vinyl ether include reacting a carboxyl group and a vinyl ether group of a polymer obtained from styrenes and maleic acids as monomers with a catalyst or without a catalyst to obtain a blocked carboxylic acid (hemiacetal ester).

[0038] Examples of alcohol compounds having no carbon-carbon double bond or carbon-carbon triple bond include aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, t-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol; alkylene oxide-derived monoalcohols such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monobutyl ether; and alcohols having a phenolic hydroxyl group such as 4-hydroxybenzyl alcohol and 3-hydroxybenzyl alcohol. Two or more of these may be used.

[0039] Examples of amine compounds having no carbon-carbon double bond or carbon-carbon triple bond include M-600, M-1000, M-2005, and M-2070 (all trade names, manufactured by HUNTSMAN Corporation), aniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 4-aminobenzoic acid, 4-aminosalicylic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-aminothiophenol, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 4-dodecylaniline. Two or more of these may be used. Among these alcohol compounds and amino compounds, compounds having a phenolic hydroxyl group are preferred from the viewpoint of adjusting the acid value.

[0040] Resin (A) may contain repeating units other than those represented by formula (1), formula (2), and formula (4). Examples of monomers that provide such repeating units include (meth)acrylate compounds, α-olefin compounds, and vinyl ether compounds. Among these, α-olefin compounds are preferred due to their low water absorption. Examples of (meth)acrylate compounds include (meth)acrylic acid, methyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate. Examples of vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, ethylcyclohexyl vinyl ether, and cyclohexyl vinyl ether. Examples of α-olefin compounds include monofunctional olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, as well as combinations with bifunctional olefins such as isoprene.

[0041] The photosensitive resin composition of the present invention contains a resin (A) and a photosensitizer, wherein at least one of the photosensitizers is selected from the group consisting of a photoradical polymerization initiator (hereinafter sometimes referred to as "photosensitizer (b-1)"), a photoacid generator (hereinafter sometimes referred to as "photosensitizer (b-2)"), and a naphthoquinone diazide compound (hereinafter sometimes referred to as "photosensitizer (b-3)").

[0042] The content of the resin (A) contained in the photosensitive resin composition of the present invention is preferably in the range of 10 parts by mass or more and 99 parts by mass or less, based on 100 parts by mass of the solid content contained in the photosensitive resin composition, from the viewpoint of achieving both pattern processability and reduced dielectric properties of the cured product.

[0043] The content of the photosensitizer contained in the photosensitive resin composition of the present invention is preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, based on 100 parts by mass of the solid content contained in the photosensitive resin composition, from the viewpoint of improving sensitivity during exposure. On the other hand, the content of the photosensitizer is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, based on 100 parts by mass of the solid content contained in the photosensitive resin composition, from the viewpoint of suppressing residues after development.

[0044] As the photosensitizer (b-1), 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, from the viewpoints of improving sensitivity during exposure and improving mechanical properties during heating at low temperatures, it is more preferred to contain an oxime ester compound (hereinafter sometimes referred to as "photosensitizer (b-1-1)") or a phosphine oxide compound (hereinafter sometimes referred to as "photosensitizer (b-1-2)"). The photosensitizer (b-1-1) is a compound having an oxime ester structure in the molecule, whereby a bond is cleaved or a reaction occurs to generate radicals upon exposure. The photosensitizer (b-1-2) is a compound having a phosphine oxide structure in the molecule, and an acyl group, whereby a bond is cleaved or a reaction occurs to generate radicals upon exposure.

[0045] From the viewpoint of improving sensitivity during exposure and improving mechanical properties during heating at low temperatures, the photosensitizer (b-1-1) preferably contains, in its chemical structure, at least one structure selected from the following group (I):

[0046] (I) A structure in which at least one oxime ester structure is bonded to a fused polycyclic structure, a fused polycyclic heterocyclic structure, a diphenyl sulfide structure, a structure containing a nitro group or a halogen atom, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, a furylcarbonyl structure, or a benzene structure (α-oxime structure) or a structure in which at least one oxime ester carbonyl structure is bonded to a fused polycyclic structure, a fused polycyclic heterocyclic structure, a diphenyl sulfide structure, a structure containing a nitro group or a halogen atom, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, a furylcarbonyl structure, or a benzene structure (α-oxime structure).

[0047] The fused polycyclic structure is preferably a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, an indene structure, an indane structure, a benzoindene structure, or a benzoindane structure. The fused polycyclic heterocyclic structure is preferably a carbazole structure, a dibenzofuran structure, a dibenzothiophene structure, a benzocarbazole structure, an indole structure, an indoline structure, a benzoindole structure, a benzoindoline structure, a phenothiazine structure, or a phenothiazine oxide structure. The photosensitizer (b-1-1) more preferably has a structure in which a nitro group or a halogen atom is bonded to a fused polycyclic structure, a fused polycyclic heterocyclic structure, a diphenyl sulfide structure, or a benzene structure.

[0048] From the viewpoint of photobleachability, the photosensitizer (b-1-1) preferably has a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, an indole structure, a benzoindole structure, a phenothiazine structure, a phenothiazine oxide structure, or a diphenyl sulfide structure, and also preferably has a structure in which at least one oxime ester carbonyl structure is bonded to a fused polycyclic structure, a fused polycyclic heterocyclic structure, a diphenyl sulfide structure, or a benzene structure. When the photosensitizer (b-1-1) has photobleachability, the effects of improving sensitivity during exposure and improving pattern processability in thick films become significant. Note that photobleachability refers to a decrease in absorbance at wavelengths in the ultraviolet region (e.g., 400 nm or less) or visible light wavelengths (380 to 780 nm) due to bond cleavage or reaction upon exposure.

[0049] The photosensitizer (b-1-1) as described above is presumed to improve the mechanical properties when heated at low temperatures because it has the effect of improving the degree of crosslinking of the cured product and promoting the ring-closing reaction of the resin due to the generation of radicals when heated at low temperatures and the interaction of the oxime ester structure.

[0050] Specific examples of the photosensitizer (b-1-1) include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximimino)-1-propanone, 2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, Examples include ethanone, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), NCI-831, NCI-930 (all manufactured by ADEKA), OXE-03, OXE-04 (all manufactured by BASF). 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.

[0051] Examples of the photosensitizer (b-1-2) include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide. These are thought to improve the mechanical properties when heated at low temperatures because they have the effect of improving the degree of crosslinking of the cured product and promoting the ring-closing reaction of the resin due to the generation of radicals when heated at low temperatures and the interaction of the phosphine oxide structure.

[0052] Other examples of the photosensitizer (b-1) include the photoradical polymerization initiators described in JP-A-2018-165819.

[0053] The photosensitizer (b-2) is a compound that has the property of cleaving a bond or generating an acid upon exposure. However, the photosensitizer (b-2) in the present invention does not include the photosensitizer (b-3) described below. The inclusion of the photosensitizer (b-2) is suitable for negative pattern formation from the viewpoint of promoting cationic polymerization. On the other hand, when a resin or the like has an acidic group protected by an acid-dissociable group, it is suitable for positive pattern formation from the viewpoint of liberating an alkali-soluble group upon exposure. Examples of the photosensitizer (b-2) include ionic compounds and nonionic compounds. The ionic compound is preferably a triorganosulfonium salt compound. The nonionic compound is preferably a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate ester compound, a carboxylate ester compound, a sulfonimide compound, a phosphate ester compound, or a sulfonebenzotriazole compound.

[0054] Although a known photoacid generator can be used as the photosensitizer (b-2), from the viewpoints of reactivity as an initiator for cationic polymerization and copper corrosivity, the photosensitizer (b-2) preferably contains a sulfonium salt containing at least one counter anion selected from the group consisting of borate ions, phosphate ions, and gallate ions. Here, the borate ions are complex ions having boron as the central atom, the phosphate ions are complex ions having phosphorus as the central atom, and the gallate ions are complex ions having gallium as the central atom.

[0055] Examples of the cation that forms the sulfonium salt include triphenylsulfonium, tri-p-tolylsulfonium, 1-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, bis(4-methylphenyl)sulfonio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis {4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p -tolyl sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 5-(4-ethoxyphenyl)thiaanthrenium, 5-(2,4,6-trimethylphenyl)thiaanthrenium and other triarylsulfoniums; diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium and other diarylsulfoniums;Monoarylsulfoniums such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium; including, but not limited to, dimethylphenacylsulfonium, phenacyltrhydrothiophenium, dimethylbenzylsulfonium, and benzyltetrahydrothiophenium;

[0056] Examples of borate ions include, but are not limited to, pentafluorophenylborate, trifluorophenylborate, tetrafluorophenylborate, trifluoromethylphenylborate, bis(trifluoromethyl)phenylborate, pentafluoroethylphenylborate, bis(pentafluoroethyl)phenylborate, fluoro-bis(trifluoromethyl)phenylborate, fluoro-pentafluoroethylphenylborate, and fluoro-bis(pentafluoroethyl)phenylborate.

[0057] Examples of phosphate ions include, but are not limited to, hexafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, and the like.

[0058] Gallate ions include, but are not limited to, tetrakis(pentafluorophenyl)gallate, tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate.

[0059] The photosensitizer (b-3) is a compound that undergoes a structural change upon exposure to generate an indenecarboxylic acid or a sulfoindenecarboxylic acid. The inclusion of the photosensitizer (b-3) is suitable for forming a positive pattern. The photosensitizer (b-3) is preferably a 5-naphthoquinone diazide sulfonic acid ester or a 4-naphthoquinone diazide sulfonic acid ester, which is a compound having a phenolic hydroxyl group.

[0060] Examples of the photosensitizer (b-3) include a polyhydroxy compound to which a sulfonic acid of quinone diazide is ester-bonded, a polyamino compound to which a sulfonic acid of quinone diazide is sulfonamide-bonded, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded. While not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds need to be substituted with quinone diazide, it is preferable that, on average, 40 mol% or more of the total functional groups are substituted with quinone diazide. By using such a quinone diazide compound, a positive photosensitive resin composition can be obtained that is sensitive to common ultraviolet rays, such as the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp.

[0061] Examples of polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, and BisRS- 2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, BisP-AP (product name, book Examples of suitable phenolic resins include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (all trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), and novolak resins.

[0062] The photosensitive resin composition of the present invention may further contain one or more resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, as well as polysiloxane, phenolic resin, and acrylic resin (hereinafter, these resins may be collectively referred to as "resin (C)"). The polyimide precursor referred to here refers to a resin having an amide bond or the like as a precursor moiety of an imide bond in the repeating structure of the main chain, and does not include resins such as resin (A) having an amide bond or the like as a precursor moiety of an imide bond in the side chain. Among these, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, and polysiloxane are preferred because they can provide a photosensitive resin composition with higher heat resistance. In particular, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, or copolymers thereof are particularly preferred because they further improve mechanical properties. Phenolic resins can improve photolithography properties. Acrylic resins can improve photolithography properties in negative-tone photosensitive resin compositions. The content of resin (C) contained in the photosensitive resin composition of the present invention is preferably in the range of 100 parts by mass or more and 500 parts by mass or less, based on 100 parts by mass of resin (A) contained in the photosensitive resin composition, from the viewpoint of improving heat resistance, mechanical properties, or photolithography properties.

[0063] Examples of polyimide precursors include those obtained by reacting tetracarboxylic acids and their derivatives with diamines and their derivatives. Examples of polyimide precursors include polyamic acids, polyamic acid esters, polyamic acid amides, and polyisoimides. Examples of tetracarboxylic acid derivatives include tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid activated diesters (hereinafter, these may be collectively referred to as "tetracarboxylic acids"). Examples of diamine derivatives include compounds in which the amino moiety is isocyanated or trimethylsilylated (hereinafter, these may be collectively referred to as "diamines").

[0064] The polyimide precursor may have a residue of a tetracarboxylic acid. By containing residues of other tetracarboxylic acids, various functions such as elastic modulus and adhesion can be imparted. Examples of other tetracarboxylic acids include 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-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, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 2,2-bis(3,4-dicarboxyphenyl)propane, and 2,2-bis(2,3-dicarboxyphenyl)propane. ) 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, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3,4-dicarboxybenzoic acid amide), bicyclo[2.2.2]octan-7-ene-2,3,5,6-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, or residues of their tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid active diesters. Furthermore, examples of acid anhydrides having a siloxane structure, such as anhydrides of tetracarboxylic acid (acid dianhydrides), include X-22-168AS, X-22-168A, X-22-168B, and X-22-168-P5-B (manufactured by Shin-Etsu Chemical Co., Ltd.). The polyimide precursor may have these residues either alone or in combination of two or more.

[0065] The polyimide precursor may have a residue of a diamine. By appropriately selecting the structure of the diamine, various properties can be imparted. Examples of diamines include 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, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, dimercaptophenylenediamine, 1,5-naphthalenediamine, 9,10-anthracenediamine, 4,4'-diaminobiphenyl ... Aminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)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 Pan, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, bis[(4 aromatic diamines such as bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], 4,4'-diaminodiphenyl sulfide, and 4-aminobenzoic acid 4-aminophenyl ester; ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,Aliphatic diamines such as 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, or dimer diamine, ED-600, ED-900, ED-2003, EDR-148, EDR-176, RT-1000, HE-1000, HT-1100 Examples of suitable diamines include alkylene oxide-containing diamines such as HT-1700 and HT-1700 (all trade names, manufactured by HUNTSMAN Corporation), and siloxane diamines such as bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and X-22-9409 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Aromatic diamines are preferred from the viewpoint of heat resistance, siloxane diamines are preferred from the viewpoint of adhesion, and aliphatic diamines are preferred from the viewpoint of low water absorbency.

[0066] Furthermore, since the presence of a phenolic hydroxyl group improves adhesive strength when directly bonded and reduces corrosion when the metal electrode is copper or silver, the polyimide precursor preferably contains a residue of a bisaminophenol compound. Examples of the residue of the bisaminophenol compound 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 4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, or 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane.

[0067] Furthermore, by capping the resin terminals with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid, it is possible to adjust the weight average molecular weight of the resin or introduce a functional group different from that in the molecule. Preferred examples of monoamines include the amine compounds exemplified in the explanation of formula (1). Preferred examples of acid anhydrides, acid chlorides, and monocarboxylic acids 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.

[0068] 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 (5).

[0069]

[0070] (R ２ represents a tetravalent to hexavalent organic group, R ３ represents a divalent to decavalent organic group. ５ R each independently represents a monovalent organic group having 1 to 10 carbon atoms or a hydroxyl group, and n represents an integer of 0 to 8. ４, each independently represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. m represents an integer of 2 to 4. * represents a point of attachment.) R ２ -(COOR ４ ) ｍ represents a residue of the above-mentioned tetracarboxylic acid or a derivative thereof. ３ - (R ５ ) ｎ represents a residue of the above-mentioned diamine or a derivative thereof. ４ Examples of the organic group having 1 to 30 carbon atoms include saturated hydrocarbon groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, and n-octyl; alkylene oxide groups such as 2-methoxyethyl, 2-methoxypropyl, diethylene glycol methyl, and dipropylene glycol methyl; and unsaturated bond-containing organic groups such as ethyl 2-(meth)acrylate, propyl 2-(meth)acrylate, butyl 2-(meth)acrylate, allyl, and butenyl.

[0071] Examples of polyimides include those obtained by dehydrating and ring-closing the aforementioned polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide by heating or by a reaction using an acid or a base, and have residues of tetracarboxylic acid or a derivative thereof and residues of diamine or a derivative thereof.

[0072] The polyimide may, for example, be one containing a structural unit represented by the following formula (6).

[0073]

[0074] (R ６ represents a tetravalent to decavalent organic group, and R ７ represents a divalent to octavalent organic group. ８ and R ９ represents a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different. k and l represent integers of 0 to 6. * represents a point of attachment.) R ６ - (R ８ ) ｋrepresents a residue of the above-mentioned tetracarboxylic acid or a derivative thereof. ７ - (R ９ ) ｌ represents a residue of the above-mentioned diamine or a derivative thereof.

[0075] Examples of polybenzoxazole precursors include polyhydroxyamides obtained by reacting dicarboxylic acids and derivatives thereof with diamines such as bisaminophenol compounds.

[0076] Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, dimer acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc. These compounds may be used alone or in combination of two or more.

[0077] Examples of bisaminophenols include the bisaminophenol compounds exemplified in the polyimide precursor.

[0078] The polybenzoxazole precursor may include those containing a structural unit represented by the following formula (7).

[0079]

[0080] (R １０ represents a divalent to hexavalent organic group, R １１ represents a single bond or a divalent to hexavalent organic group. １２ and R １３ Each of the symbols independently represents a monovalent organic group having 1 to 10 carbon atoms or a hydroxyl group. q and r represent integers of 0 to 4. * represents a point of attachment.) R １０ - (R １２ ) ｑ represents a residue of the above-mentioned dicarboxylic acid or a derivative thereof. １１ - (R １３ ) ｒ represents a residue of the above-mentioned bisaminophenol compound or a derivative thereof.

[0081] 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.

[0082] The polybenzoxazole may include those containing a structural unit represented by formula (8).

[0083]

[0084] (R １４ represents a divalent to hexavalent organic group, R １５ represents a tetravalent to hexavalent organic group. １６ and R １７ Each independently represents a monovalent organic group having 1 to 10 carbon atoms or a hydroxyl group. o represents an integer of 0 to 4, and p represents an integer of 0 to 2. * represents a point of attachment.) R １４ - (R １６ ) о R represents a residue of the above-mentioned dicarboxylic acid or a derivative thereof. In particular, a dimer acid residue is preferred from the viewpoint of achieving a low dielectric loss tangent. １５ - (R １７ ) ｐ represents a residue of the above-mentioned bisaminophenol compound or a derivative thereof.

[0085] 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.

[0086] Examples of phenols constituting novolak 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, Examples thereof include catechol, 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 as a mixture thereof.

[0087] 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.

[0088] 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.

[0089] From the viewpoint of achieving low dielectric constant, novolak resins or resol resins having a rigid naphthalene structure or biphenyl structure are more preferred, and specifically, it is preferred to use p-phenylphenol, α-naphthol, or β-naphthol 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-7851H (trade name, manufactured by Meiwa Kasei Co., Ltd.), with GPH-65, GPH-103, and MEHC-7851H having a rigid structure being particularly preferred.

[0090] The polysiloxane may be a hydrolysis condensate of at least one organosilane compound. Examples of the organosilane compound include tetrafunctional silanes such as tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-hexyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, trifluoromethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Examples of the silane include trifunctional silanes such as methoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, and 2-fluorenyltrimethoxysilane; bifunctional silanes such as dimethyldimethoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, and di(1-naphthyl)dimethoxysilane; and monofunctional silanes such as trimethylmethoxysilane and (3-glycidoxypropyl)dimethylmethoxysilane. Compounds in which the methoxysilane moiety is replaced with ethoxysilane or acetoxysilane can also be used. Two or more of these organosilanes may be used.

[0091] 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.

[0092] 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 necessary and sufficiently. It is also possible to leave a certain amount of silanol groups remaining.

[0093] 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.

[0094] 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.

[0095] The synthesis method of the acrylic resin includes radical polymerization of a (meth)acrylic compound. Known (meth)acrylic compounds may be used, such as (meth)acrylic compounds containing a carboxyl group and / or an acid anhydride group, or other (meth)acrylic acid esters. Known catalysts for radical polymerization may be used, such as azo compounds such as azobisisobutyronitrile or organic peroxides such as benzoyl peroxide.

[0096] The photosensitive resin composition of the present invention may further contain a crosslinking agent. The content of the crosslinking agent contained in the photosensitive resin composition of the present invention is preferably in the range of 3 parts by mass or more and 80 parts by mass or less, when the total amount of resin (A) and resin (C) contained in the photosensitive resin composition is taken as 100 parts by mass, from the viewpoint of exhibiting the effect of the crosslinking agent. The crosslinking agent has two effects: one is to react with active species generated by the photosensitizer to improve the sensitivity of the photosensitive resin composition; and the other is to improve the properties (glass transition temperature (Tg), elastic modulus, chemical resistance, etc.) of the cured product obtained by curing the photosensitive resin composition. The crosslinking agent can be contained for the purpose of achieving either or both of these effects.

[0097] The crosslinking agent may be a compound having two or more polymerizable unsaturated bond groups for the purpose of improving sensitivity (however, resin (A) is excluded from the crosslinking agent referred to in the present invention). A compound having two or more polymerizable unsaturated bond groups can be expected to not only improve exposure sensitivity but also improve adhesion, heat resistance, etc. depending on its structure. Specific examples of crosslinking agents include pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, and tripentaerythritol octaacrylate when it is desired to further improve exposure sensitivity; dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate, and 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene when it is desired to improve adhesion during development by improving hydrophobicity; and tetraethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate when it is desired to improve the elongation of the cured product. Furthermore, from the viewpoint of improving adhesion after curing, epoxy(meth)acrylate obtained by reacting a polyfunctional epoxy compound with (meth)acrylic acid can be used.

[0098] Examples of crosslinking agents that are contained mainly for the purpose of improving the properties (Tg, modulus of elasticity, chemical resistance, etc.) of the cured product include, but are not limited to, methylol compounds, epoxy compounds, and oxetane compounds.

[0099] The epoxy compound may contain known compounds, and specific examples thereof include bisphenol A diglycidyl ether, cresol novolac resin-type polyfunctional glycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, etc. Specific examples thereof include 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.), Epiclon EXA-9583, Epiclon N666, Epiclon N695, HP4032, HP72 00 (all trade names, manufactured by DIC Corporation), Techmore VG3101L (trade name, manufactured by Printec Co., Ltd.), Tepic S, Tepic G, Tepic P, Tepic VL (all trade names, manufactured by Nissan Chemical Industries, Ltd.), Epotohto YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), GAN, GOT, EPPN502H, NC3000 or NC6000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), YDPN-638, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A (trade names, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and the like.

[0100] 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.), or oxetanized phenol novolak.

[0101] 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.).

[0102] The photosensitive resin composition of the present invention preferably contains a reaction inhibitor, and particularly preferably contains a reaction inhibitor represented by formula (9).

[0103]

[0104] (R １８ and R １９ are each independently a hydrogen atom, a fluorine atom, or —CF ３ , -NO ２ or -NO, with the proviso that R １８ and R １９ At least one of the groups is a fluorine atom, —CF ３ , -NO ２ Or -NO. s represents 0 or 1.) When S=0, the rational formula is C ６ H ３ (R １８ ) (R １９ ) (OH).

[0105] This reaction inhibitor has the effect of suppressing the reaction of the polymerizable reactive groups (carbon-carbon double bonds or carbon-carbon triple bonds) of the resin (A) when the photosensitive resin composition applied to a substrate is prebaked. Therefore, it has the effect of improving the sensitivity of the photosensitive resin composition. In the photosensitive resin composition of the present invention, the content of the reaction inhibitor is preferably in the range of 0.002 parts by mass to 1.5 parts by mass, more preferably in the range of 0.01 parts by mass to 1.0 parts by mass, and even more preferably in the range of 0.01 parts by mass to 0.2 parts by mass. When the content is within this range, improved patterning properties with an alkaline developer can be expected when used in a photosensitive resin composition.

[0106] The reaction inhibitor that can be used in the present invention is not particularly limited, and any known reaction inhibitor can be used, as long as it has the effect of inhibiting the reaction of the polymerizable reactive group (carbon-carbon double bond or carbon-carbon triple bond) of the resin (A) when the photosensitive resin composition applied to the substrate is prebaked. Examples of the reaction inhibitor represented by formula (9) include 2-nitrophenol, 4-nitrophenol, and 2-nitroso-1-naphthol.

[0107] Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition can be obtained by mixing and dissolving the resin (A), the photosensitizer, and, if necessary, the resin (C), the crosslinking agent, the solvent, the curing accelerator, the adhesion improver, the surfactant, and the like.

[0108] When dissolving the resin (A), photosensitizer, and other components in a solvent, examples of the dissolution method include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, typically 25°C to 80°C. The order in which the components are dissolved is not particularly limited, and examples include a method in which the components are dissolved in order starting with the least soluble compound. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the photosensitive resin composition, typically 200 rpm to 2000 rpm. Heating may be performed as needed even when stirring, typically 25°C to 80°C. For components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of the other components due to the generation of bubbles.

[0109] The photosensitive resin composition thus obtained is preferably filtered through a filter to remove dust and particles. The filter pore size may be, for example, 10.0 μm, 5.0 μm, 3.0 μm, 1.0 μm, 0.5 μm, 0.2 μm, or 0.1 μm, but is not limited thereto. The filter material may be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), with polyethylene or nylon being preferred.

[0110] Next, the cured product of the present invention will be described. The cured product of the present invention is obtained by curing the resin (A) or photosensitive resin composition of the present invention. The method for producing the cured product includes a step of applying the resin (A) or photosensitive resin composition of the present invention and drying it to form a resin film, a step of forming a pattern if necessary, and a step of thermally crosslinking the resin by heat treatment (curing).

[0111] In the process of forming a resin film by applying and drying the resin (A) or photosensitive resin composition of the present invention, the resin (A) or photosensitive resin composition of the present invention is first applied to a substrate to obtain a coating film of the photosensitive resin composition. Examples of the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and these substrates on which circuit components are arranged.

[0112] Examples of the coating method include spin coating, slit coating, dip coating, spray coating, printing, etc. The coating thickness varies depending on the coating method, the solids concentration of the composition, the viscosity, etc., but the coating is usually carried out so that the film thickness after drying is 0.1 to 150 μm.

[0113] Prior to coating, the substrate to which the resin (A) or photosensitive resin composition is to be applied may be pretreated with the adhesion improver described above. Examples of pretreatment methods include treating the substrate surface by spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment, or the like using a solution in which 0.5 to 20% by mass of the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. After treating the substrate surface, a vacuum drying treatment may be performed, if necessary. Furthermore, the reaction between the substrate and the adhesion improver may then be promoted by heat treatment at 50°C to 280°C.

[0114] Next, the coating film of resin (A) or the photosensitive resin composition is dried to form a resin film. Drying is preferably carried out using an oven, a hot plate, infrared rays, or the like at a temperature in the range of 50°C to 140°C for 1 minute to 2 hours.

[0115] Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. Alternatively, pattern exposure may be performed without using a mask using a laser light source with a wavelength of 300 nm to 500 nm.

[0116] To form a pattern of the photosensitive resin composition film, after exposure, exposed or unexposed areas are removed using a developer. Since the resin (A) of the present invention has a carboxyl group, an alkaline aqueous solution can be used as the developer, but an organic solvent may also be used. When the developer is an alkaline aqueous solution, examples of alkaline compounds used as the solute include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, may be added alone or in combination to these aqueous alkaline solutions.

[0117] When the developer is an organic solvent, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent, is preferred. For example, preferred good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. After development, it is preferable to perform a rinsing treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, examples include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, rinsing treatment may be carried out by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to the water.

[0118] After development, a temperature of 150°C to 320°C is applied to promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. The lower limit of the curing conditions in the present invention is preferably 170°C or higher, but more preferably 180°C or higher to ensure sufficient curing. The upper limit of the curing conditions is preferably 250°C or lower, more preferably 230°C or lower. Examples of heating methods for curing include heating using an oven, hot plate, infrared radiation, a flash annealing device, or a laser annealing device. Examples of the treatment atmosphere include an air, oxygen, nitrogen, helium, neon, argon, krypton, or xenon atmosphere, a gas atmosphere containing 1.0 to less than 10,000 ppm by mass (0.00010 to 1.0% by mass) of oxygen, a gas atmosphere containing 10,000 ppm by mass or more (1.0% by mass) of oxygen, and a vacuum.

[0119] The cured product of the present invention can be used as an insulating film or a protective film. Specific examples of the insulating film or protective film include, but are not limited to, a passivation film for a semiconductor, a surface protective film for a semiconductor element, an interlayer insulating film, an interlayer insulating film for multilayer wiring for high-density mounting, and an insulating layer for an organic electroluminescent device.

[0120] The electronic component of the present invention comprises a cured product of the resin (A) or a cured product of the photosensitive resin composition described in the present invention. Examples of the electronic component include active components having semiconductors, such as transistors, diodes, integrated circuits (ICs), and memories, and passive components, such as resistors, capacitors, inductors, and antenna elements. Electronic components using semiconductors are also called semiconductor devices.

[0121] Specific examples of uses of the cured product in electronic components include semiconductor passivation films, surface protective films for semiconductor elements, TFTs (Thin Film Transistors), and other interlayer insulating films, such as interlayer insulating films between rewirings in multilayer wiring for high-density packaging of 2 to 10 layers, and insulating films and protective films for touch panels. However, the present invention is not limited to these and can have a variety of structures. The substrate on which the cured product is formed can be appropriately selected depending on the application and process, and examples include silicon, ceramics, glass, metal, and epoxy resin, and multiple substrates may be arranged on the same surface. The cured product of the present invention has low dielectric constant, dielectric dissipation factor, and water absorption, which allows for reduced signal attenuation and delay in electronic components that handle high frequencies.

[0122] The electronic component of the present invention comprises the cured product of the present invention disposed as an insulating film between wirings, and by disposing the cured product of the present invention as an insulating film between wirings, a multilayer wiring structure can be formed in which two or more layers of rewiring are electrically separated by an insulating film made of the cured product of the photosensitive resin composition of the present invention.

[0123] Among the electronic components of the present invention, examples of semiconductor devices include chip-first fan-out wafer-level packages and chip-first fan-out panel-level packages. Chip-first fan-out wafer-level packages and chip-first fan-out panel-level packages are semiconductor packages in which an extension section is provided around a semiconductor chip using an encapsulating resin such as epoxy resin, rewiring is performed from electrodes on the semiconductor chip to the extension section, and solder balls are also mounted on the extension section to ensure the required number of terminals. In chip-first fan-out wafer-level packages and chip-first fan-out panel-level packages, wiring is installed so as to straddle the boundary formed by the main surface of the semiconductor chip and the main surface of the encapsulating resin, and a cured product is arranged as an insulating film between the wiring.

[0124] As an example of the method for manufacturing an electronic component of the present invention, a method for manufacturing a semiconductor device using a redistribution layer (RDL) first process is shown. A barrier metal such as Ti is formed on a support substrate such as a glass substrate or a silicon wafer by sputtering, a Cu seed (seed layer) is further formed on top of that by sputtering, and then electrode pads made of Cu are formed by plating. Next, the photosensitive resin composition of the present invention is applied to the entire surface of the support substrate on which the electrode pads have been formed and dried to form a resin film. If necessary, a line-and-space, square, or hole pattern is formed in the resulting resin film. A heat treatment is then performed to form a cured layer. This layer becomes an insulating film. Next, a seed layer is formed again by sputtering, and metal wiring (redistribution wiring) made of Cu is formed by plating. Subsequently, the seed layer process through the metal wiring formation process are repeated to form a multilayer wiring structure. Next, the photosensitive resin composition of the present invention is again applied and patterned, followed by heat treatment and curing to form an insulating film. Then, Cu posts are formed on the metal wiring in the openings of the insulating film using a plating method. The pitch of the Cu posts and the pitch of the conductive portions of the semiconductor chip are made equal. That is, the pitch of the conductive portions of the semiconductor chip is finer than the pitch of the electrode pads, and each rewiring layer constituting the multilayer wiring structure gradually becomes finer pitch from the electrode pads to the Cu posts, thereby multiplying the wiring. The thickness of adjacent insulating films in the multilayer wiring structure also becomes the same or thinner as they approach the semiconductor chip. Next, the semiconductor chip is connected to the Cu posts via solder bumps. This electrically connects the electrode pads and the semiconductor chip via the metal wiring and solder bumps. The semiconductor chip is then encapsulated with an encapsulating resin to form a semiconductor package, and the support substrate and the rewiring layer are peeled off to separate the semiconductor package. In this way, a semiconductor device having a multilayer wiring structure using the RDL first process can be obtained.

[0125] Other examples of the electronic component of the present invention include an antenna element, a composite of an antenna element and a semiconductor device, etc. Examples of antenna elements using the cured film of the present invention include those similar to those described in International Publication No. 2021 / 020344, the contents of which are incorporated herein by reference.

[0126] For example, Figure 1 is a schematic diagram of a coplanar-feed microstrip antenna, which is a type of planar antenna. The antenna can be obtained by, for example, applying the photosensitive resin composition of the present invention to copper foil, pre-baking, exposing it to light, laminating copper foil, and thermally curing it to form a cured film having copper foil on both sides. This can then be patterned by a subtractive method. The planar antenna of Figure 1 has an antenna pattern of copper wiring in a microstrip line (MSL).

[0127] Next, the antenna pattern of FIG. 1 will be described. An insulating film 36, which serves as the antenna substrate, is formed on the entire surface of the ground 35. The antenna portion 31, matching circuit 32, and MSL feed line 33 are formed on the insulating film. The ground wiring thickness J and antenna wiring thickness K can be any thickness depending on the impedance design, but are typically 2 to 20 μm. To match the impedance between the antenna portion 31 and the feed line 33, the length M of the matching circuit 32 is 1 / 4 × λr (λr = (wavelength of transmitted radio wave) / [1 / 2 × (dielectric constant of insulating material)]). The width W and length L of the antenna portion 31 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. Furthermore, due to these characteristics, an antenna element using the insulating film of the present invention is suitable for high-frequency antennas, and the area (= L × W) of the antenna portion can be set to 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.

[0128] The display device of the present invention comprises a cured product of the resin (A) or a cured product of the photosensitive resin composition described in the present invention. Examples of the display device include liquid crystal display devices, organic EL display devices, and μLED display devices. Specific examples of the cured product in the display device include a protective film (which also serves as a planarizing film) and an insulating film on a thin film transistor (TFT) array substrate, but are not limited thereto and can have a variety of structures. The cured product of the present invention has a low dielectric constant and water absorption, which can reduce parasitic capacitance and improve transistor characteristics.

[0129] The present invention will be described below with reference to examples, but the present invention should not be construed as being limited by these examples. First, the evaluation methods used in each example and comparative example will be described. Furthermore, before the evaluation, the varnish was filtered through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore size of 1 μm. Here, the term "varnish" refers to a liquid prepared by dissolving resin (A) and, if necessary, a photosensitizer, resin (C) or crosslinking agent in a solvent.

[0130] (1) Molecular Weight Measurement The weight average molecular weight (Mw) was confirmed using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nippon Waters Co., Ltd.). Measurement was performed using N-methyl-2-pyrrolidone as the developing solvent, and the weight average molecular weight (Mw) was calculated in terms of polystyrene.

[0131] (2) Measurement of Acid Value The acid value (unit: mgKOH / g) of a solution obtained by dissolving a resin in PGMEA was measured by potentiometric titration in accordance with JIS K2501 (2003) using an automatic potentiometric titrator (AT-510; manufactured by Kyoto Electronics Manufacturing Co., Ltd.) and a 0.1 mol / L sodium hydroxide / ethanol solution as a titration reagent and a xylene / dimethylformamide = 1 / 1 (weight ratio) as a titration solvent.

[0132] (3) Solubility Test A solution of resin dissolved in N-methyl-2-pyrrolidone was spin-coated onto a silicon wafer and dried at 120°C for 3 minutes to form a 3 μm thick coating film, which was then immersed for 60 seconds in a 10.0 wt% KOH aqueous solution, a 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution (NMD-3; manufactured by Mitsubishi Gas Chemical Company, Inc.), or a 0.045 wt% KOH aqueous solution, and then removed and rinsed with water for 30 seconds. The coating film was rated as A if it dissolved in all three types of developers, B if it dissolved in two types of developers, C if it dissolved in only one type of developer, and D if it did not dissolve in any of the developers.

[0133] (4) Measurement of dielectric constant and dielectric loss tangent of resin A solution of resin dissolved in N-methyl-2-pyrrolidone was applied to a 6-inch silicon wafer by spin coating using a Mark-7 coater / developer so that the film thickness after pre-baking at 120°C for 3 minutes would be 11 μm, and the wafer was then pre-baked. Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the wafer was heated to 230°C at a rate of 3.5°C / min at an oxygen concentration of 20 ppm or less, and then heat-treated at 230°C for 1 hour. After the treatment, the wafer was cooled, and when the temperature reached 50°C or less, the silicon wafer was removed and immersed in 45% by mass hydrofluoric acid for 5 minutes to peel off the resin film from the silicon wafer. The 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 at room temperature of 23.0°C and humidity of 45.0% RH using a perturbation cavity resonator method in accordance with ASTM D2520. The dielectric properties were evaluated on a 5-point scale as shown in Table 1 below.

[0134]

[0135] (5) Measurement of Resin Heat Resistance (Glass Transition Point) A resin film was prepared in the same manner as in "(4) Measurement of Dielectric Constant and Dielectric Tangent" above. The resin film obtained by this method was cut into 3.0 cm x 1.5 cm pieces using a single-edged blade. The resin 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. The evaluation criteria were as follows: A higher glass transition point indicates higher heat resistance of the film. A: Glass transition point of 150°C or higher B: Glass transition point of 120°C or higher but lower than 150°C C: Glass transition point of 100°C or higher but lower than 120°C D: Glass transition point of less than 100°C

[0136] (6) Metal Adhesion Evaluation: A substrate (copper-plated substrate) was prepared by sputtering titanium and copper to a thickness of 100 nm onto a silicon wafer, followed by electrolytic plating to form a 2 μm-thick copper-plated film on its surface. A solution of resin dissolved in N-methyl-2-pyrrolidone was spin-coated onto this substrate using a spinner (Mikasa Co., Ltd.). The substrate was then baked at 120°C for 3 minutes using a hot plate (D-SPIN, Dai-Nippon Screen Mfg. Co., Ltd.), ultimately producing a pre-baked film with a thickness of 11 μm. These films were heated to 230°C at a rate of 3.5°C / min in an inert oven CLH-21CD-S (Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, and then heat-treated at each temperature for 1 hour to obtain a resin film. A single-edged blade was used to make a 10-by-10 grid-like incision at 2 mm intervals into the resin film. The resin film with the cuts was peeled off using Scotch tape (registered trademark), and the number of peeled squares out of 100 was counted to evaluate the adhesion properties between the metal material and the resin film. In the evaluation of adhesion properties, if the number of peeled squares of the resin film was 0, it was rated as extremely good (A), if it was 1 to less than 10, it was rated as good (B), if it was 11 to less than 20, it was rated as fair (C), and if it was 20 or more, it was rated as poor (D).

[0137] (7) Pattern Processability (7)-1 Sensitivity A varnish of the photosensitive resin composition was spin-coated onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at 120°C for 3 minutes to produce a pre-baked film with a thickness of 11 μm. The resulting pre-baked film was exposed to light by contact exposure through a grayscale mask (having a 1:1 line and space pattern of 1 to 100 μm) for sensitivity measurement 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. The film was then post-exposure baked at 120°C for 1 minute, and puddle-developed for 90 seconds using a 2.38% by mass aqueous TMAH developer using a MARK-7 coater / developer, followed by rinsing with water for 30 seconds.

[0138] After development, the film thickness was measured, and in the case of a negative photosensitive resin composition, the film thickness after pre-baking was taken as 100%, and the minimum exposure amount at which the remaining film ratio of the exposed area exceeded 90% was defined as the sensitivity (mJ / cm ２ When the photosensitive resin composition is a positive type, the minimum exposure dose and sensitivity at which the film thickness of the exposed area becomes 5 nm or less (below the detection limit) were used. The exposure dose was measured with an i-line illuminometer.

[0139] (7)-2 Resolution The minimum pattern dimension (μm) after development was measured at the exposure dose at the sensitivity determined in (7)-1.

[0140] (8) Measurement of the dielectric constant and dielectric loss tangent of the film obtained from the photosensitive resin composition The measurement was carried out in the same manner as in "(4) Measurement of the dielectric constant and dielectric loss tangent of the resin" above, except that the material to be coated was a varnish of the photosensitive resin composition instead of a "solution of the resin dissolved in N-methyl-2-pyrrolidone". However, in the case of a negative photosensitive resin composition, after pre-baking, the film was coated with PLA at 300 mJ / cm2 over the entire surface. ２ The dielectric properties were evaluated on a 5-point scale as shown in Table 2 below.

[0141]

[0142] (9) Measurement of heat resistance (glass transition point) of film obtained from photosensitive resin composition The measurement was carried out in the same manner as in "(5) Measurement of glass transition point of resin" above, except that the material to be coated was a varnish of a photosensitive resin composition instead of a solution of a resin dissolved in N-methyl-2-pyrrolidone. However, in the case of a negative photosensitive resin composition, after pre-baking, the film was coated with PLA at 300 mJ / cm2 over the entire surface. ２ The film was exposed to light at an intensity of 100°C. The evaluation criteria were as follows: the higher the glass transition temperature, the higher the heat resistance of the film. A: Glass transition point value is 200°C or higher B: Glass transition point value is 170°C or higher and lower than 200°C C: Glass transition point value is 140°C or higher and lower than 170°C D: Glass transition point value is lower than 140°C.

[0143] (10) Measurement of elongation at break (elongation) of film obtained from photosensitive resin composition A film was prepared in the same manner as in "(4) Measurement of dielectric constant and dielectric dissipation factor" above, except that the material to be coated was a varnish of a photosensitive resin composition instead of a "solution of a resin dissolved in N-methyl-2-pyrrolidone." This film was cut into strips of 1.5 cm in width and 9 cm in length, and using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the film was pulled 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 (%). However, in the case of a negative photosensitive resin composition, after pre-baking, the film was subjected to a tensile test at 300 mJ / cm2 on the entire surface using PLA. ２ The specimen was exposed to light at an intensity of 1000 kJ / s. Measurements were made on 10 strips per specimen, and the average of the top five highest numerical values ​​was calculated from the results. Elongation at break of 30% or more was rated as excellent (A), 20% or more but less than 30% as good (B), 10% or more but less than 20% as fair (C), and less than 10% as poor (D).

[0144] (11) Evaluation of chemical resistance of films obtained from photosensitive resin compositions A varnish of the photosensitive resin composition was applied to a silicon wafer by spin coating using a spinner, and then baked at 120°C for 3 minutes using a hot plate to finally prepare a pre-baked film having a thickness of 11 µm. In the case of negative type films, these films were coated on the entire surface of the coating film using PLA at 500 mJ / cm. ２The film was exposed to light at an intensity of 1000 kJ / s, and in the case of a positive-tone film, the film was heated to 230°C at a rate of 3.5°C / min in an inert oven CLH-21CD-S at an oxygen concentration of 20 ppm or less, and then heated for 1 hour at each temperature to obtain a film. The film was then immersed in an organic chemical (dimethyl sulfoxide: 25% TMAH aqueous solution = 92:8) at 40°C for 10 minutes, and the presence or absence of elution was observed. As a result, if the film thickness change rate before and after treatment was less than 10%, it was evaluated as good (A), if it was 10% to less than 20%, it was evaluated as fair (B), and if it was 20% or more, it was evaluated as poor (C).

[0145] The abbreviations for the compounds used in the Synthesis Examples, Examples, and Comparative Examples are listed below: HEMA: 2-hydroxyethyl (meth)acrylate BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane MAP: 4-aminophenol ODPA: 4,4'-oxydiphthalic anhydride HA: 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane DFA: dimethylformamide dimethyl acetal BFE: 1,2-bis(4-formylphenyl)ethane NA: 5-norbornene-2,3-dicarboxylic anhydride.

[0146] Synthesis Example 1 Synthesis of Resin (A-1) In a nitrogen atmosphere, 15.6 g (0.15 mol) of styrene as monomers and 34.3 g (0.35 mol) of maleic anhydride were added to 200 g of orthoxylene as a solvent and 0.25 g of normal dodecylbenzenesulfonic acid as a surfactant, and the mixture was heated to 135°C in a separable flask. Next, 25.6 g of di-t-butyl peroxide as a radical polymerization initiator was added to this mixture over 1.5 hours. Thereafter, the mixture was further reacted at 135°C for 2.5 hours to obtain a styrene-maleic anhydride copolymer.

[0147] 49.9 g of the resulting styrene-maleic anhydride copolymer was placed in a 1 L separable flask, followed by the addition of 45.6 g (0.35 mol) of HEMA and 400 ml of γ-butyrolactone and stirring at room temperature. 8.15 g of pyridine was then added with stirring to obtain a reaction mixture. After the reaction ceased to generate heat, the mixture was allowed to cool to room temperature and left for 16 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of isopropanol and filtered to produce a precipitate. This was redissolved in 1.5 L of tetrahydrofuran, and the solution was again added dropwise to 14 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum dried to obtain powdered resin (A-1). The weight-average molecular weight (Mw) was 8,000. A nuclear magnetic resonance spectrometer (JNM-ECZ400R, manufactured by JEOL Ltd.) was used to identify the structure of the resulting resin. The results are shown below. １ H-NMR (dimethyl sulfoxide-d6): 12.2 (br, 1H), 7.2 (m, 5H), 6.4 (s, 1H), 6.6 (s, 1H), 4.3-4.4 (m, 4H), 2.8-2.9 (m, 2H), 2.6 (m, 3H), 2.0 (s, 1H), 1.8 (m, 2H).

[0148] Synthesis Example 2: Synthesis of Resin (A-2)

[0047] The same procedure as in Synthesis Example 1 was repeated except that the amount of styrene used was changed to 26.0 g (0.25 mol), the amount of maleic anhydride was changed to 24.5 g (0.25 mol), and the amount of HEMA was changed to 32.5 g (0.25 mol), to obtain Resin (A-2). The weight average molecular weight (Mw) was 10,000.

[0149] Synthesis Example 3: Synthesis of Resin (A-3)

[0063] The same procedure as in Synthesis Example 1 was repeated except that the amounts of styrene, maleic anhydride, and HEMA used were changed to 39.1 g (0.375 mol), 12.3 g (0.125 mol), and 16.3 g (0.125 mol), respectively, to obtain Resin (A-3). The weight average molecular weight (Mw) was 11,000.

[0150] Synthesis Example 4 Synthesis of Resin (A-4) Resin (A-4) was obtained in the same manner as in Synthesis Example 1, except that the amount of styrene used was 46.9 g (0.45 mol), the amount of maleic anhydride was 4.90 g (0.05 mol), and the amount of HEMA was 6.51 g (0.05 mol). The weight average molecular weight (Mw) was 12,000.

[0151] Synthesis Example 5 Synthesis of Resin (A-5) In a nitrogen atmosphere, 15.6 g (0.15 mol) of styrene as monomers and 34.3 g (0.35 mol) of maleic anhydride were added to 200 g of orthoxylene as a solvent and 0.25 g of normal dodecylbenzenesulfonic acid as a surfactant, and the mixture was heated to 135°C in a separable flask. Next, 25.6 g of di-t-butyl peroxide as a radical polymerization initiator was added to this mixture over 1.5 hours. Thereafter, the mixture was further reacted at 135°C for 2.5 hours to obtain a styrene-maleic anhydride copolymer.

[0152] 49.9 g of the resulting styrene-maleic anhydride copolymer was placed in another separable flask, followed by 41.7 g (0.35 mol) of 4-aminostyrene and 100 g of γ-butyrolactone, and the mixture was stirred at room temperature to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and stand for 16 hours to obtain a reaction solution. The resulting reaction solution was added to 3 L of isopropanol and filtered to produce a precipitate. This was redissolved in 1.5 L of tetrahydrofuran, and the solution was again added dropwise to 14 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum-dried to obtain powdered resin (A-5). The weight-average molecular weight (Mw) was 8,000. The weight-average molecular weight (Mw) was 13,000. A nuclear magnetic resonance spectrometer (JNM-ECZ400R, manufactured by JEOL Ltd.) was used to identify the structure of the resulting resin. The results are shown below. １ H-NMR (DMSO): 12.2 (br, 1H), 10.1 (s, 1H), 7.9 (d, 2H), 7.6 (d, 2H), 7.2 (m, 5 H), 6.5 (m, 1H), 5.7 (d, 1H), 5.3 (d, 1H), 2.6 (m, 3H), 2.3 (t, 1H), 1.8 (m, 2H).

[0153] Synthesis Example 6: Synthesis of Resin (A-6)

[0063] The same procedure as in Synthesis Example 5 was repeated, except that the amounts of styrene, maleic anhydride, and 4-aminostyrene were changed to 46.9 g (0.45 mol), 4.90 g (0.05 mol), and 5.96 g (0.05 mol), respectively, to obtain Resin (A-6). The weight average molecular weight (Mw) was 12,000.

[0154] Synthesis Example 7 Synthesis of Resin (A-7) Resin (A-7) was obtained in the same manner as in Synthesis Example 5, except that the amounts of styrene, maleic anhydride, and 4-aminostyrene were changed to 26.0 g (0.25 mol), 24.5 g (0.25 mol), and 29.8 g (0.25 mol), respectively. The weight average molecular weight (Mw) was 10,000.

[0155] Synthesis Example 8: Synthesis of Resin (A-8)

[0063] Resin (A-8) was obtained in the same manner as in Synthesis Example 7, except that 29.8 g of 4-aminostyrene was replaced with 29.3 g (0.25 mol) of 4-aminophenylacetylene. The weight average molecular weight (Mw) was 10,000.

[0156] Synthesis Example 9: Synthesis of Resin (A-9)

[0063] Resin (A-9) was obtained in the same manner as in Synthesis Example 7, except that 23.8 g (0.20 mol) of 4-aminostyrene and 13.1 g (0.05 mol) of 4-dodecylaniline were used instead of 29.8 g of 4-aminostyrene. The weight average molecular weight (Mw) was 10,000.

[0157] Table 3 summarizes the characteristics of resins (A-1) to (A-9).

[0158] Synthesis Example 10: Synthesis of naphthoquinone diazide compound Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. To this solution, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound having the following structure.

[0159]

[0160] (* indicates a bonding point.) Synthesis Example 11 Synthesis of Acrylic Resin (C-1) 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMEA) were charged into a 500 ml flask. 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 the mixture was heated and stirred at 70 °C for 5 hours. Next, 12.7 g of glycidyl methacrylate, 1 g of dimethylbenzylamine (a different addition catalyst is preferred), 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution and heated and stirred at 90 °C for 4 hours to obtain a solution of acrylic resin (C-1). The weight average molecular weight (Mw) was 13,000.

[0161] Synthesis Example 12 Synthesis of Polysiloxane (C-2) Under a dry nitrogen stream, a 500 ml three-necked 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 of methyl silicate 51 (equivalent to 0.05 moles of Si atom), and 155.04 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 0.515 g of phosphoric acid (0.30 parts by mass relative to the charged monomers) in 54.45 g of water was added over 10 minutes with stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and the oil bath was then 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 mixture was then heated and stirred for 2 hours (internal temperature: 100°C), yielding a solution of polysiloxane (C-2). The weight-average molecular weight (Mw) was 6,000.

[0162] Synthesis Example 13 Synthesis of Polyimide (C-3) 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 N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as "NMP") were weighed and dissolved in a three-neck flask. To this was added a solution of 31.02 g (0.10 mol; 100 mol% based on all structural units derived from carboxylic acids and their derivatives) 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 resulting solid precipitate 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 (C-3). The weight average molecular weight (Mw) was 25,000.

[0163] Synthesis Example 14 Synthesis of Polyimide Precursor (C-4) 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 (C-4). The weight average molecular weight (Mw) was 24,000.

[0164] Synthesis Example 15 Synthesis of Polybenzoxazole Precursor (C-5) 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), 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, followed by stirring 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. The mixture was then 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 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 precursor (C-5). The weight-average molecular weight (Mw) was 19,000.

[0165] Varnishes of Examples 1 to 31 and Comparative Examples 1 to 9 were prepared under yellow light according to the composition ratios shown in Table 4, and evaluations (2) to (6) were carried out for Examples 1 to 9 and Comparative Examples 1 and 2, and evaluations (7) to (11) were carried out for Examples 10 to 31 and Comparative Examples 3 to 9. The measurement results are shown in Tables 5 and 6, respectively.

[0166]

[0167]

[0168] <Resin (A)> (A-1) to (A-9): Resins corresponding to Synthesis Examples 1 to 9, respectively <Photosensitizer> NCI-831: Photoradical polymerization initiator manufactured by ADEKA Corporation (corresponding to photosensitizer (b-1)) CPI-310B: Photoacid generator manufactured by San-Apro Ltd. (corresponding to photosensitizer (b-2)) NQD: Naphthoquinone diazide compound described in Synthesis Example 10 (corresponding to photosensitizer (b-3)) <Resin (C)> (C-1) to (C-5): Resins corresponding to Synthesis Examples 11 to 15, respectively MEHC-7851H: Phenolic resin manufactured by Meiwa Kasei Co., Ltd. Styrene polymer: Polystyrene resin manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. <Crosslinking agent> DPHA: Dipentaerythritol pentaacrylate TEPIC-VL: Isocyanuric acid-modified epoxy compound (manufactured by Nissan Chemical Industries, Ltd.) MOM: HMOM-TPHAP (manufactured by Honshu Chemical Co., Ltd.) <Reaction inhibitor> 2Ni-1Naph: 2-nitroso-1-naphthol <Solvent> PGMEA: propylene glycol monomethyl ether acetate GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone

[0169]

[0170]

[0171] 31 Antenna section 32 Matching circuit 33 MSL feeding circuit 34 Feeding point 35 Ground 36 Insulating film

Claims

1. A resin having at least a repeating unit represented by formula (1) and a repeating unit represented by formula (2), in which the repeating unit represented by formula (1) accounts for 30 mol % or more and less than 100 mol % when the total amount of repeating units contained in the resin is taken as 100 mol %. (R １ represents a hydrogen atom or a methyl group.) (X １ represents -O- or -NH-. １ represents a monovalent organic group having 2 to 30 carbon atoms and a carbon-carbon double bond or a carbon-carbon triple bond.

2. X in the formula (2) １ is -NH-, and Y １ The resin according to claim 1 , wherein is a group represented by formula (3). (Ar represents a divalent aromatic ring having 6 to 18 carbon atoms. Y ２ represents a vinyl group or an ethynyl group. * represents X １ represents the point of attachment to 3. The resin according to claim 1 or 2, having an acid value of 50 mg KOH / g or more and 200 mg KOH / g or less.

4. The resin according to claim 1 or 2, further comprising a repeating unit represented by formula (4). (X ２ represents -O- or -NH-. １ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms and having no carbon-carbon double bonds or carbon-carbon triple bonds.

5. A cured product obtained by curing the resin according to claim 1 or 2.

6. A photosensitive resin composition comprising the resin according to claim 1 or 2 and a photosensitizer, wherein at least one of the photosensitizers is a compound selected from the group consisting of a photoradical polymerization initiator, a photoacid generator and a naphthoquinone diazide compound.

7. The photosensitive resin composition according to claim 6, further comprising one or more resins selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, copolymers thereof, polysiloxanes and phenolic resins.

8. The photosensitive resin composition according to claim 6, further comprising a crosslinking agent.

9. The photosensitive resin composition according to claim 6, further comprising a reaction inhibitor represented by formula (9). (R １８ and R １９ each independently represents a hydrogen atom, a fluorine atom, or -CF ３ , -NO ２ or -NO, where R １８ and R １９ At least one of the groups is a fluorine atom, -CF ３ , -NO ２ Or -NO. s represents 0 or 1.

10. A cured product obtained by curing the photosensitive resin composition according to claim 6.

11. An electronic part comprising the cured product according to claim 5.

12. A display device comprising the cured product according to claim 5.

13. An electronic part comprising the cured product according to claim 10.

14. A display device comprising the cured product according to claim 10.

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