JP2023147245A - Photosensitive resin composition, cured product and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition that is excellent in low dielectric loss tangent when being formed into a cured product, and can suppress cracking after a reliability test of a device to which the cured product is applied.SOLUTION: A photosensitive resin composition contains (A) a polyfunctional monomer, (B) an alkali-soluble resin and (C) a photopolymerization initiator, wherein (A) the polyfunctional monomer contains a compound represented by formula (1) and/or a compound represented by formula (2), (B) the alkali-soluble resin contains one or more selected from the group consisting of (B1) polyimide having a structural unit represented by formula (3), (B2) a polyimide precursor having a structural unit represented by formula (4), and (B3) a polybenzoxazole precursor having a structural unit represented by formula (5) and a copolymer thereof, fluorine atom concentration in (B1) the polyimide having the structural unit represented by formula (3) is 0.1 mass% or more and 10 mass% or less, and fluorine atom concentration in (B2) the polyimide precursor having the structural unit represented by formula (4) is 0.1 mass% or more and 10 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition, a cured product, and an electronic component. More specifically, the present invention relates to a photosensitive resin composition suitable for use in surface protective films and interlayer insulating films of electronic components such as semiconductor devices, insulating layers of organic electroluminescent devices, and the like.

Typical materials for surface protection films and interlayer insulating films of semiconductor devices, insulating layers of organic electrolytic devices, and flattening films of TFT substrates include polyimide resins that have excellent heat resistance, electrical insulation, and the like. Furthermore, in order to improve the productivity, studies are being conducted on polyimides imparted with negative or positive photosensitivity and their precursors.

In recent years, as the applications of semiconductors have expanded and their performance has improved, efforts have been made to reduce costs and increase integration by increasing the efficiency of manufacturing processes. Therefore, attention is being focused on semiconductor devices that form multilayer metal rewiring. The insulating film of such multilayer metal rewiring requires multiple high-temperature treatment processes in the manufacturing process. Furthermore, pattern processability by photolithography is required to improve productivity. Furthermore, in high-frequency communication device applications for high-speed wireless communication, a reduction in dielectric loss tangent in an insulating film is required in order to reduce transmission loss. Therefore, pattern processability, high mechanical properties as a cured product, heat resistance, low dielectric loss tangent, and reliability in devices to which the cured product is applied are required. Examples of insulating films having sufficient heat resistance include resin compositions containing resins such as polyimide and polybenzoxazole and thermal crosslinking agents (Patent Document 1). As a method of imparting pattern processability, a polyimide precursor having a specific chemical structure introduced into the side chain can be used (Patent Document 2). As a method of imparting resistance to flux treatment in the solder bump formation process, stripper process in the wiring formation process, etc., a resin composition in which a specific thermosetting resin is added is cited (Patent Document 3).

Japanese Patent Application Publication No. 2007-16214 Japanese Patent Application Publication No. 2011-59656 JP2012-63498A

When conventional technology is applied to a multilayer wiring insulating film for a high-frequency communication device for high-speed wireless communication, the cured products of the compositions described in Patent Document 1, Patent Document 2, and Patent Document 3 have a dielectric constant and a dielectric loss tangent. There were also problems in that the reduction was insufficient and cracks were observed in the cured product after reliability tests.

In order to solve the above problems, the present invention relates to the following.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a polyfunctional monomer, (B) an alkali-soluble resin, and (C) a photopolymerization initiator,
The (A) polyfunctional monomer contains a compound represented by formula (1) and/or a compound represented by formula (2),
The alkali-soluble resin (B) includes (B1) a polyimide having a structural unit represented by formula (3), (B2) a polyimide precursor having a structural unit represented by formula (4), and (B3) a polyimide precursor having a structural unit represented by formula (4). 5) Contains one or more types selected from the group consisting of polybenzoxazole precursors having the structural unit represented by and copolymers thereof,
The fluorine atom concentration in the polyimide having the structural unit represented by the formula (3) (B1) is 0.1% by mass or more and 10% by mass or less,
The fluorine atom concentration in the polyimide precursor having the structural unit represented by formula (4) (B2) is 0.1% by mass or more and 10% by mass or less.

In formula (1), W ¹ and W ² each independently represent a monovalent organic group having 2 to 25 carbon atoms and having a carbon-carbon double bond. In formula (1), a, b, c, and d are natural numbers that each independently satisfy a+b=6 to 17 and c+d=8 to 19, and the broken line portion is a carbon-carbon single bond or a carbon-carbon double bond. means.

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

In formula (3), X ¹ represents a tetravalent organic group having 2 to 100 carbon atoms, Y ¹ represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ¹ and at least one of Y ¹ has a fluorine atom. R ⁵ represents a phenolic hydroxyl group. * indicates a bonding group.

In formula (4), X ² represents a tetravalent organic group having 2 to 100 carbon atoms, Y ² represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ² At least one of Y 2 and Y ² has a fluorine atom. R ⁷ represents a phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group having 1 to 20 carbon atoms or a hydrogen atom. * indicates a bonding group.

In formula (5), X ³ represents a divalent aliphatic group having 10 to 20 carbon atoms, R ⁸ represents a single bond or a divalent to hexavalent organic group having 1 to 100 carbon atoms, and R ⁹ represents a carbon Indicates a monovalent organic group of numbers 1 to 10. r represents an integer from 0 to 4. * indicates a bonding group.

The cured product of the photosensitive resin composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and can further suppress cracking after a reliability test of a device to which the cured product is applied.

The photosensitive resin composition of the present invention includes (A) a polyfunctional monomer (hereinafter sometimes referred to as component (A)), and (B) an alkali-soluble resin (hereinafter sometimes referred to as component (B)). ) and (C) a photopolymerization initiator (hereinafter sometimes referred to as component (C)), the photosensitive resin composition comprising:
The (A) polyfunctional monomer contains a compound represented by formula (1) and/or a compound represented by formula (2),
The alkali-soluble resin (B) is a polyimide having a structural unit represented by the formula (3) (B1) (hereinafter sometimes referred to as the component (B1)), and (B2) a polyimide having a structural unit represented by the formula (4). A polyimide precursor having a structural unit (hereinafter sometimes referred to as the (B2) component), a polybenzoxazole precursor having a structural unit represented by (B3) formula (5) (hereinafter referred to as the (B3) component) ), and copolymers thereof,
The fluorine atom concentration in the polyimide having the structural unit represented by the formula (3) (B1) is 0.1% by mass or more and 10% by mass or less,
The fluorine atom concentration in the polyimide precursor having the structural unit represented by formula (4) (B2) is 0.1% by mass or more and 10% by mass or less.

In formula (1), W ¹ and W ² each independently represent a monovalent organic group having 2 to 25 carbon atoms and having a carbon-carbon double bond. In formula (1), a, b, c, and d are natural numbers that each independently satisfy a+b=6 to 17 and c+d=8 to 19, and the broken line portion is a carbon-carbon single bond or a carbon-carbon double bond. means.

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

In formula (3), X ¹ represents a tetravalent organic group having 2 to 100 carbon atoms, Y ¹ represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ¹ and at least one of Y ¹ has a fluorine atom. R ⁵ represents a phenolic hydroxyl group. * indicates a bonding group.

In formula (4), X ² represents a tetravalent organic group having 2 to 100 carbon atoms, Y ² represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ² At least one of Y 2 and Y ² has a fluorine atom. R ⁷ represents a phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group having 1 to 20 carbon atoms or a hydrogen atom. * indicates a bonding group.

In formula (5), X ³ represents a divalent aliphatic group having 10 to 20 carbon atoms, R ⁸ represents a single bond or a divalent to hexavalent organic group having 1 to 100 carbon atoms, and R ⁹ represents a carbon Indicates a monovalent organic group of numbers 1 to 10. r represents an integer from 0 to 4. * indicates a bonding group.

The photosensitive resin composition of the present invention contains component (A). By including the component (A), the component (C) causes a crosslinking reaction with active species generated by exposure, resulting in a negative pattern. Further, a cured product obtained by curing the photosensitive composition has a low dielectric constant and a low dielectric loss tangent, and can suppress cracking after a reliability test of a device to which the cured product is applied.

The component (A) contains a compound represented by formula (1) and/or a compound represented by formula (2). The compound represented by formula (1) and/or the compound represented by formula (2) is a photopolymerizable monomer, and is produced by the reaction of a dimer acid or its derivative with a compound having a carbon-carbon double bond. can get.

Dimer acid is a known dibasic acid obtained by intermolecular polymerization reaction of unsaturated fatty acids, and is obtained by dimerizing unsaturated fatty acids having 11 to 22 carbon atoms. The main component of industrially obtained dimer acids is dibasic acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, but depending on the degree of purification, It may contain amounts of 18 carbon monomer acids, 54 carbon trimer acids and other polymerized fatty acids from 20 to 54 carbon atoms.

Examples of dimer acid derivatives include dimer diol in which all carboxyl groups of the dimer acid are primary hydroxy groups, dimer diamine in which all carboxyl groups are primary amino groups, dimer thiol in primary thiol groups, and dimer isocyanate in which all carboxyl groups are primary hydroxy groups. Further examples include epoxy compounds and oxetane compounds obtained by reacting these functional groups.

The compound having a carbon-carbon double bond further contains one functional group capable of reacting with a dimer acid derivative. Specific functional groups include amino groups, hydroxy groups, carboxyl groups or substituents of salts thereof, epoxy groups, acid anhydride groups, and isocyanate groups. By reacting these functional groups with the functional groups of the dimer acid or its derivative, a compound represented by formula (1) and/or a compound represented by formula (2) is obtained.

Specific examples of compounds having a carbon-carbon double bond include N-(4-aminophenyl)maleimide, 4-aminostyrene, 3-aminostyrene, 2-aminostyrene, 3-amino-1-propene, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2-propyl alcohol, 2-(meth)acrylamidoethyl alcohol, methylol Vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl (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 Alcohols having one ethylenically unsaturated bond and one hydroxyl group, such as -2-hydroxypropyl phthalate, 2-vinylbenzyl alcohol, 3-vinylbenzyl alcohol, and 4-vinylbenzyl 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, Ethylene such as glycerin-1-allyloxy-2-methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), 2-(acryloyloxy)-2-(hydroxymethyl)butyl methacrylate Alcohols having two or more sexually unsaturated bonds and one hydroxyl group, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, acrylic anhydride, Methacrylic anhydride, itaconic anhydride, maleic anhydride, 4-pentene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 2-acryloyloxyethyl isocyanate, 2-methacryloyl Examples include oxyethyl isocyanate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Here, "(meth)acrylate" refers to methacrylate or acrylate. The same applies to similar notations.

Commercially available dimer acids include Haridimer 200, Haridimer 270S (trade names, manufactured by Harima Kasei Co., Ltd.), Td-205 (W), and Td-395 (trade names, Tsukino Foods). (manufactured by Kogyo Co., Ltd.), Pripol 1004, Pripol 1006, Pripol 1009, Pripol 1013, Pripol 1017, and Pripol 1040 (trade names, manufactured by Croda Japan Co., Ltd.).

As a dimer acid derivative, commercially available dimer diols include Pespol HP-1000 (trade name, manufactured by Toagosei Co., Ltd.) and Pripol 2023 (trade name, manufactured by Croda Japan Co., Ltd.). Commercially available products of dimer diamine include Versamine 551, Versamine 552 (all trade names, manufactured by BASF Japan Ltd.), Priamine 1071, Priamine 1073, Priamine 1074, and Priamine 1075 (all trade names, manufactured by Croda Japan Ltd.). can be mentioned.

In addition, from the viewpoint of exposure sensitivity, in the formula (1) and the formula (2), at least one of W ¹ and W ² and at least one of W ³ and W ⁴ are determined by formula (6), formula (7), A group represented by formula (8) or formula (9) is preferable.

In formula (6), formula (7), formula (8) and formula (9), K ¹ , K ² , K ³ , K ⁴ , L ¹ and L ² each independently represent -NH-, -O- , -CH ₂ - or -S-. R ¹ and R ³ each independently represent a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. R ² and R ⁴ each independently represent a single bond or a divalent organic group having 1 to 5 carbon atoms. i and j each independently represent an integer of 1 to 5. * indicates a bonding point.

In the formula (1) and the formula (2), at least one of W ¹ and W ² and at least one of W ³ and W ⁴ are formula (6), formula (7), formula (8), or formula (9). ) Formula (11) etc. are mentioned as a specific example of the (A) component which is a group represented by.

In addition, from the viewpoint of reducing dielectric properties, in the formula (1) and the formula (2), at least one of W ¹ and W ² and at least one of W ³ and W ⁴ correspond to the formula (6) or the formula (7). In the group represented by formula (6) and formula (7), K ¹ , K ² , L ¹ and L ² are preferably -NH-.

Furthermore, in the formula (1) and the formula (2), at least one of W ¹ and W ² and at least one of W ³ and W ⁴ are represented by formula (12), formula (13), formula (14), or A group represented by formula (15) is more preferable.

* indicates a bonding point.

Component (A) is preferably prepared in a range of 5% by mass or more and 50% by mass or less based on 100% by mass of the photosensitive resin composition.

The method for producing component (A) is not particularly limited, and known synthesis methods such as addition reaction or condensation reaction can be used. An example of a specific manufacturing method is shown below.
In the first step, a compound having a carbon-carbon double bond and one functional group capable of reacting with a dimer acid derivative is charged into a reaction vessel under a nitrogen atmosphere and stirred. At this time, if necessary, a solvent may be added, and a reaction catalyst or a reaction promoter may also be added.
As the solvent, it is preferable to use a solvent having a solubility parameter of 10 or less according to Fedor's method. Specific examples include, but are not limited to, toluene and propylene glycol methyl ether acetate. It may also contain two or more types of solvents.

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

In the second step, the dimer acid derivative is added dropwise to the stirring solution prepared in the first step, and the mixture is stirred until the reaction is completed. As the dimer acid derivative, the above-mentioned commercial products are preferred. If the heat of reaction is large, cooling may be performed during dropping, if necessary.
As a third step, after the reaction is completed, component (A) is obtained by removing the solvent of the prepared solution using an evaporator. Furthermore, when a reaction catalyst or a reaction promoter is used, it is preferable to remove it by liquid separation treatment or silica gel chromatography.
Component (A) in the present invention can be identified using a nuclear magnetic resonance apparatus (NMR) or the like.

NMR is a process that occurs when a material is placed in a strong magnetic field and pulsed radio waves are irradiated onto molecules with their spins aligned in the same direction, causing nuclear magnetic resonance, and then the molecules return to their original stable state. This is an analysis method that detects signals and analyzes molecular structures. The most commonly used NMR analysis is ^{the 1H} -NMR spectrum, in which the environment in which the hydrogen atom is located is determined from the chemical shift of the peak, the number of hydrogen atoms is determined from the integral value, and the number of adjacent protons is determined from the splitting of the peak. It is possible to obtain information about the molecular structure, such as its effects. As an example showing characteristic chemical shifts, the chemical shift of hydrogen bonded to an allylic carbon is 1.5-2 ppm, the chemical shift of a hydrogen atom bonded to an alkene is 4.5-6 ppm, and the chemical shift of hydrogen bonded to an aromatic ring is 1.5-2 ppm. The chemical shift of atoms appears at 6-9 ppm, and the chemical shift of hydrogen bonded to the amide group appears at 5-11 ppm.

The photosensitive resin composition of the present invention contains component (B).
By appropriately selecting the component (B), it is possible to control the characteristics of the photosensitive resin composition and the characteristics of the cured product obtained by curing it.
The component (B) includes (B1) a polyimide having a structural unit represented by formula (3), (B2) a polyimide precursor having a structural unit represented by formula (4), and (B3) a polyimide precursor having a structural unit represented by formula (5). Containing one or more types selected from the group consisting of a polybenzoxazole precursor having a structural unit represented by, and a copolymer thereof,
The fluorine atom concentration in the polyimide having the structural unit represented by the formula (3) (B1) is 0.1% by mass or more and 10% by mass or less,
The fluorine atom concentration in the polyimide precursor having the structural unit represented by formula (4) (B2) is 0.1% by mass or more and 10% by mass or less.

In formula (3), X ¹ represents a tetravalent organic group having 2 to 100 carbon atoms, Y ¹ represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ¹ and at least one of Y ¹ has a fluorine atom. R ⁵ represents a phenolic hydroxyl group. * indicates a bonding group.

In formula (4), X ² represents a tetravalent organic group having 2 to 100 carbon atoms, Y ² represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ² At least one of Y 2 and Y ² has a fluorine atom. R ⁷ represents a phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group having 1 to 20 carbon atoms or a hydrogen atom. * indicates a bonding group.

In formula (5), X ³ represents a divalent aliphatic group having 10 to 20 carbon atoms, R ⁸ represents a single bond or a divalent to hexavalent organic group having 1 to 100 carbon atoms, and R ⁹ represents a carbon Indicates a monovalent organic group of numbers 1 to 10. r represents an integer from 0 to 4. * indicates a bonding group.

Particularly from the viewpoint of pattern processability, the component (B) preferably contains a polyimide precursor having a structural unit represented by the formula (B2) (4). In particular, from the viewpoint of suppressing cracks after a reliability test, it is preferable to contain a polybenzoxazole precursor having a structural unit represented by formula (B3) (5).

Furthermore, the storage stability of the photosensitive resin composition can be improved by sealing the terminal end of the resin with a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, or the like. Further, from the viewpoint of reducing dielectric properties due to a ring-closing reaction with a diamine having a phenolic hydroxyl group, it is more preferable to seal the resin terminal with a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.

It is preferable that the alkali-soluble resin (B) has one or more types of structures represented by formula (10).

In formula (10), W ⁵ represents a monovalent organic group having 1 to 20 carbon atoms that does not have an amino group, and W ⁶ represents a monovalent organic group having 1 to 20 carbon atoms that does not have a carboxyl group. W ⁷ represents a divalent organic group having 3 to 20 carbon atoms and having no carboxyl group. * ¹ indicates a bond with a carbon atom, * ² indicates a bond with a hydrogen atom or a carbon atom, * ³ and * ⁴ indicate a bond with a nitrogen atom, * ⁵ indicates a hydrogen atom, a bond with a carbon atom, Indicates a bond with an atom, nitrogen atom, or oxygen atom.

In particular, from the viewpoint of improving the heat resistance of the cured product, the component (B) preferably has a crosslinkable terminal structure having a polymerizable unsaturated bond, and the component (B) is represented by formula (10). and in the formula (10), W ⁵ is a monovalent C2-C20 structure having a polymerizable unsaturated bond and having no amino group. is an organic group, W ⁶ is a monovalent organic group having 2 to 20 carbon atoms and has a polymerizable unsaturated bond and no carboxyl group, and W ⁷ is a polymerizable unsaturated bond. More preferably, it is a divalent organic group having 3 to 20 carbon atoms and having a saturated bond and no carboxyl group. Furthermore, from the viewpoint of reducing dielectric properties, it is more preferable to adopt a structure in which the bonding portion * ³ and the carbonyl group are bonded in the formula (10).

As the monoamine, known monoamines such as 4-aminophenol can be used. In particular, from the viewpoint of improving the heat resistance of the cured product, 3-amino-1-propyne, 3-amino-1-propene, 3-amino-2-methyl-1-propene, 4-aminostyrene, and 4-aminophenyl acetylene are used. preferable.

As the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound, known acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds such as phthalic anhydride can be used.

In particular, from the viewpoint of improving the heat resistance of cured products, itaconic anhydride, nadic anhydride, 4-ethynyl phthalic anhydride, 4-(methylethynyl) phthalic anhydride, 4-phenylethynylphthalic anhydride, acryloyl Preferred are chloride, tigloyl chloride, cinnamoyl chloride and linoleoyl chloride. In addition, from the viewpoint of reducing dielectric properties due to a ring-closing reaction with a diamine having a phenolic hydroxyl group, it is preferable to seal the resin terminal with a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Specifically, acryloyl chloride , tigloyl chloride, cinnamoyl chloride, linoleoyl chloride, and the like are preferred.

Furthermore, from the viewpoint of pattern processability, dielectric properties of the cured product, and crack suppression after reliability testing, component (B) is a diamine residue having a phenolic hydroxyl group in 100 mol% of all diamine residues in component (B). It is preferable to have the group in the range of 30 mol% or more and 90 mol% or less, and more preferably in the range of 30 mol% or more and 85 mol% or less.

As the component (B1), for example, a structure represented by formula (3) is obtained by dehydrating and ring-closing polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide by heating or reaction using an acid or a base. Examples include those having a tetracarboxylic acid and/or its derivative residue, and a diamine and/or its derivative residue.

The component (B1) includes a tetracarboxylic acid and/or its derivative residue corresponding to X ¹ in formula (3), and a diamine and/or corresponding to Y ¹ (R ⁵ ) ₂ in formula (3). or at least one of its derivative residues has a fluorine atom, and the fluorine atom concentration in component (B1) is 0.1% by mass or more and 10% by mass or less. By having the fluorine atom concentration in the component (B1) within the above range, it is possible to achieve both reduction in dielectric properties and suppression of cracks after a reliability test. Further, in component (B1), the diamine and/or its derivative residue has a phenolic hydroxyl group, so that component (B) becomes soluble in an aqueous alkaline solution.

In formula (3), X ¹ represents a tetravalent organic group having 2 to 100 carbon atoms, Y ¹ represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ¹ and at least one of Y ¹ has a fluorine atom. R ⁵ represents a phenolic hydroxyl group. * indicates a bonding group.

When X ¹ in formula (3) has a fluorine atom, examples of the fluorine atom-containing tetracarboxylic acid or derivative residue thereof include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis( 3,4-dicarboxybenzoic acid amide), or their tetracarboxylic dianhydrides, tetracarboxylic dichlorides, or tetracarboxylic active diesters thereof. These residues may be contained alone or in combination of two or more in the component (B1).

Component (B1) may have a known tetracarboxylic acid residue or its derivative residue that does not have a fluorine atom. Specific residues of tetracarboxylic acids or derivatives thereof include, for example, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8 -Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)methane, carboxyphenyl)ethane, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2'-bis[4-(3,4 -dicarboxyphenoxy)phenyl]propane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 2,3,5,6-pyridinetetracarboxylic acid or 3,4, 9,10-perylenetetracarboxylic acid, bicyclo[2.2.2]octan-7-ene-2,3,5,6-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1, 2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid or 2,3,4,5-tetrahydrofurantetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid Examples include acids or their residues such as tetracarboxylic dianhydrides, tetracarboxylic dichlorides, or tetracarboxylic active diesters. These residues may be contained alone or in combination of two or more in the component (B1).

When Y ¹ in formula (3) has a fluorine atom, examples of the residue of a diamine or its derivative having a fluorine atom include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,2-bis[3-(3-aminobenzamide)- Examples include residues such as 4-hydroxyphenyl]hexafluoropropane, or compounds whose amine moieties are isocyanated or trimethylsilylated. Moreover, these residues may be contained alone or in combination of two or more kinds in the component (B1).

In addition, when Y ¹ in formula (3) does not have a fluorine atom, examples of the residue of a diamine or its derivative having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)ether, (3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4 -hydroxyphenyl] sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis[N-(3-aminobenzoyl)-3- Amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl) ) Fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4- hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino- 1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3 '-Diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'- Biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane or 2,2-bis(3-amino-4-hydroxyphenyl)propane, etc. Examples include residues. These residues may be contained alone or in combination of two or more kinds in component (B1).

Component (B1) may have a residue of a known diamine and/or a derivative thereof that does not have a fluorine atom or a phenolic hydroxyl group. Specific examples of residues of diamines or derivatives thereof that do not have a fluorine atom or a phenolic hydroxyl group include m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl, Bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4' -diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'- Tetramethyl-4,4'-diaminobiphenyl, dimercaptophenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 4,4'-diaminobenzanilide, 3,4' -diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]ether , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl) ) Sulfone, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-amino Benzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl) Benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino- 2-Benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5- benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6 -Benzoxazolyl], 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane , ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6- Diaminohexane, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Examples include diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, dimer diamine, and residues of compounds whose amine moieties are isocyanated or trimethylsilylated. These residues may be contained alone or in combination of two or more kinds in the component (B1).

Component (B2) is a thermosetting resin, and by thermosetting at high temperature and dehydration ring closure, a highly heat-resistant imide bond is formed and polyimide can be obtained. Therefore, by incorporating polyimide having a highly heat-resistant imide bond into the resin composition, the heat resistance of the resulting cured product can be significantly improved. Therefore, it is suitable when the cured product is used in applications requiring high heat resistance. In addition, component (B2) is a resin whose heat resistance improves after dehydration and ring closure, so it is suitable for use in applications where it is desired to achieve both the characteristics of the precursor structure before dehydration and ring closure and the heat resistance of the cured product.

Examples of the component (B2) include those having a structural unit represented by the formula (4) (B2) obtained by reacting a tetracarboxylic acid and its derivative with a diamine and its derivative. As the component (B2), for example, polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide having a structural unit represented by formula (4) (B2) can be mentioned.

The component (B2) includes a tetracarboxylic acid and/or its derivative residue corresponding to X ² in formula (4), and a diamine and/or corresponding to Y ² (R ⁷ ) ₂ in formula (4). or at least one of its derivative residues has a fluorine atom, and the fluorine atom concentration in component (B2) is 0.1% by mass or more and 10% by mass or less. By having the fluorine atom concentration in the component (B2) within the above range, it is possible to achieve both reduction in dielectric properties and suppression of cracks after a reliability test. In addition, component (B2) becomes soluble in an alkaline aqueous solution because the diamine and/or its derivative residue has a phenolic hydroxyl group.

In formula (4), X ² represents a tetravalent organic group having 2 to 100 carbon atoms, Y ² represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and X ² At least one of Y 2 and Y ² has a fluorine atom. R ⁷ represents a phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group having 1 to 20 carbon atoms or a hydrogen atom. * indicates a bonding group.
Furthermore, from the viewpoint of dielectric properties of the cured product and suppression of cracks after reliability tests, the diamine residue having a phenolic hydroxyl group is in the range of 30 mol% or more and 60 mol% or less out of 100 mol% of all diamine residues in component (B2). It is more preferable to have .

Further, particularly from the viewpoint of pattern processability, it is more preferable that R ⁶ in formula (4) is a monovalent organic group having 1 to 4 carbon atoms or a hydrogen atom. When R ⁶ is a monovalent organic group having 1 to 4 carbon atoms, from the viewpoint of pattern processability, R ⁶ is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, More preferred is an isobutyl group or a tert-butyl group.

When X ² in formula (4) has a fluorine atom, examples of the residue of the fluorine atom-containing tetracarboxylic acid or its derivative include those mentioned above. These residues may be contained alone or in combination of two or more kinds in component (B2).

Component (B2) may have the above-mentioned known tetracarboxylic acid residue and/or residue of a derivative thereof that does not have a fluorine atom. These residues may be contained alone or in combination of two or more kinds in component (B2).

When Y ² in formula (4) has a fluorine atom, examples of the residue of the diamine or its derivative having a fluorine atom include those mentioned above. These residues may be contained alone or in combination of two or more kinds in component (B2).

When Y ² in formula (4) does not have a fluorine atom, examples of the diamine residue having a phenolic hydroxyl group include those mentioned above. These residues may be contained alone or in combination of two or more kinds in component (B2).

Component (B2) may contain the residues of known diamines and derivatives thereof that do not have the aforementioned fluorine atom and phenolic hydroxyl group. These residues may be contained alone or in combination of two or more kinds in component (B2).

In the formula (4), when two R ⁶ each independently represent a monovalent organic group having 1 to 20 carbon atoms, X ² (COOR ⁶ ) ₂ represents a tetracarboxylic acid diester residue.
As a method for producing a tetracarboxylic acid diester, it is possible to directly react the tetracarboxylic dianhydride and alcohol in a solvent, but it is preferable to use a reaction activator from the viewpoint of reactivity. Examples of the reaction activator include tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine, and 1,8-diazabicycloundecene. The amount of the reaction activator added is preferably 3 mol% or more and 300 mol% or less, more preferably 20 mol% or more and 150 mol% or less, based on the acid anhydride group to be reacted. Further, a small amount of a polymerization inhibitor may be used for the purpose of preventing ethylenically unsaturated bond sites from crosslinking during the reaction. Thereby, in the reaction between an alcohol having an ethylenically unsaturated bond with low reactivity and a tetracarboxylic dianhydride, the reaction can be promoted by heating in a range of 120° C. or lower. Examples of the polymerization inhibitor include phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. The amount of the polymerization inhibitor added is preferably 0.1 mol% or more and 5 mol% or less of the phenolic hydroxyl group of the polymerization inhibitor relative to the ethylenically unsaturated bond of the alcohol.

The alcohol to be reacted with the tetracarboxylic dianhydride can be appropriately selected according to various purposes such as adjustment of exposure sensitivity and adjustment of solubility in organic solvents. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, i-pen. Aliphatic alcohols such as tanol or ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Examples include monoalcohols derived from alkylene oxides such as monoethyl ether and tripropylene glycol monobutyl ether.

Examples of alcohols having ethylenically unsaturated bonds include (meth)acrylates having hydroxyl groups or unsaturated fatty acid-modified alcohols. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2-propyl alcohol, 2-(meth)acrylamide ethyl 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 Acrylate, alcohol having one ethylenically unsaturated bond and one hydroxyl group such as 2-(meth)acryloxyethyl-2-hydroxypropyl phthalate, glycerin-1,3-di(meth)acrylate, glycerin-1,2- Di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin-1-allyloxy-3-methacrylate, glycerin-1-allyloxy-2- Two or more ethylenically unsaturated bonds, such as methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), and 2-(acryloyloxy)-2-(hydroxymethyl)butyl methacrylate. and alcohols having one hydroxyl group.

Examples of the unsaturated fatty acid denatured alcohol include unsaturated fatty acid denatured alcohols having 6 or more carbon atoms. Specific examples of unsaturated fatty acid denatured alcohols include 5-hexen-1-ol, 3-hexen-1-ol, 6-hepten-1-ol, cis-5-octen-1-ol, cis-3-octen-1 -ol, cis-3-nonen-1-ol, cis-6-nonen-1-ol, 9-decan-1-ol, cis-4-decan-1-ol, 10-undecen-1-ol, 11 -dodecane-1-ol, elidolinoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and erucyl alcohol.

In particular, from the viewpoint of pattern processability, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol and t-butanol are more preferred.

When the total of all carboxylic acids and all carboxylic esters in the component (B2) is 100 mol%, the ratio of all the carboxylic esters in the component (B2) is defined as the esterification rate of the component (B2). At this time, from the viewpoint of pattern processability and storage stability, the esterification rate of component (B2) is preferably in the range of 10 mol% or more and 40 mol% or less. In addition, in the case of a copolymer having a structural unit represented by formula (4), the total of all carboxylic acids and all carboxylic acid esters in the copolymer having a structural unit represented by formula (4) is 100 mol. %, the proportion of all carboxylic acid esters in the copolymer having the structural unit represented by formula (4) is the esterification rate of the copolymer having the structural unit represented by formula (4). .

The esterification rate in the present invention can be easily derived from NMR measurements and the like. Specifically, the peak intensity derived from all aromatic ring hydrogens in the polyimide precursor and the ester groups of all the carboxylic acid esters in all the tetracarboxylic acids and their derivative residues, and all the dicarboxylic acids and their derivative residues. One method is to compare the peak intensities derived from hydrogen of directly bonded hydrocarbons.

Component (B3) is a thermosetting resin, and by thermosetting at high temperature and dehydration ring closure, a highly heat resistant and rigid benzoxazole ring is formed, and polybenzoxazole is obtained. Therefore, by incorporating a polybenzoxazole having a highly heat resistant and rigid benzoxazole ring into a resin composition, the heat resistance of the resulting cured product can be significantly improved. Therefore, it is suitable when the cured product is used in applications requiring high heat resistance. In addition, since component (B3) is a resin whose heat resistance improves after dehydration and ring closure, it is suitable for use in applications where it is desired to achieve both the characteristics of the precursor structure before dehydration and ring closure and the heat resistance of the cured product.

As the component (B3), for example, a polyhydroxyamide having a structural unit represented by formula (5) obtained by reacting a dicarboxylic acid or its derivative with a bisaminophenol compound or the like as a diamine can be mentioned.

As for the component (B3), if the number of carbon atoms in the dicarboxylic acid residue is 10 to 20, the occurrence of cracks after the reliability test can be suppressed.

In formula (5), X ³ represents a divalent aliphatic group having 10 to 20 carbon atoms, R ⁸ represents a single bond or a divalent to hexavalent organic group having 1 to 100 carbon atoms, and R ⁹ represents a carbon Indicates a monovalent organic group of numbers 1 to 10. r represents an integer from 0 to 4. * indicates a bonding group.

^X3 represents a dicarboxylic acid residue. Examples of dicarboxylic acid residues in which X ³ is a divalent aliphatic group having 10 to 20 carbon atoms include 1,10-decanedicarboxylic acid, brassylic acid, 1,12-dodecanedicarboxylic acid, pentadecanedioic acid, Residues such as thapsic acid, heptadecanedioic acid, octadecanedioic acid or nonadecanedioic acid may be mentioned.

Furthermore, the storage stability of the photosensitive resin composition can be improved by sealing the resin terminal with a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, or the like. Further, from the viewpoint of reducing dielectric properties due to a ring-closing reaction with a diamine having a phenolic hydroxyl group, it is more preferable to seal the resin terminal with a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.

In addition, from the viewpoint of improving the heat resistance of the cured product, component (B3) contains 10 mol of dicarboxylic acid residues consisting of aliphatic groups having 10 to 20 carbon atoms in 100 mol% of all dicarboxylic acid residues in component (B3). % or more and 50 mol% or less.

The component (B3) can have a structural unit other than the structural unit that can be represented by formula (5). Examples of dicarboxylic acid residues in which X ³ is not a divalent aliphatic group having 10 to 20 carbon atoms include terephthalic acid, isophthalic acid, dimer acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, and biphenyl. Mention may be made of residues such as dicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid. These residues may be contained alone or in combination of two or more in component (B3).

R ⁸ (R ⁹ ) _r represents a bisaminophenol residue. Examples of R ⁸ (R ⁹ ) _r 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) sulfone, -amino-4-hydroxyphenyl)propane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-amino benzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino- 4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2,5- Diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4, 4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl) )-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3 -amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,2- Examples include residues such as bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane.

Moreover, the component (B) may be a copolymer with polyamide.

Examples of the polyamide include those obtained by dehydration condensation of a dicarboxylic acid and a diamine compound by reaction using polyphosphoric acid, and containing a structural unit represented by the following formula (16).

In formula (16), X ⁴ and Y ⁴ represent a divalent organic group. X ⁴ represents the above-mentioned dicarboxylic acid and/or its derivative residue, and Y ⁴ represents the above-mentioned diamine compound and/or its derivative residue other than the bis-aminophenol compound. * indicates a bonding point.

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

The photosensitive resin composition of the present invention contains component (C). By containing component (C), active species that initiate the crosslinking reaction of component (A) are generated during exposure, and pattern processing becomes possible through the subsequent development step. Component (C) is not particularly limited as long as it is a compound that generates radicals upon exposure to light, but alkylphenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, oxime ester compounds, and benzoic acid ester compounds are most sensitive. , is preferred because of its excellent stability and ease of synthesis. Among these, alkylphenone compounds and oxime ester compounds are preferred from the viewpoint of sensitivity, and oxime ester compounds are particularly preferred. Further, in the case of a thick film having a processed film thickness of 5 μm or more, a phosphine oxide compound is preferable from the viewpoint of resolution.

As the alkylphenone compound, known compounds can be included. For example, 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl α-Aminoalkylphenone compounds such as -phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-hydroxy-2-methyl-1 Examples include α-hydroxyalkylphenone compounds such as -phenylpropan-1-one, α-alkoxyalkylphenone compounds such as 4-benzoyl-4-methylphenylketone, and acetophenone compounds such as pt-butyldichloroacetophenone.

Among these, 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4 α-Aminoalkylphenone compounds such as -yl-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 are preferred because of their high sensitivity.

As the aminobenzophenone compound, known ones can be included. Examples include 4,4-bis(dimethylamino)benzophenone.
Examples of diketone compounds include known ones such as benzyl.
Examples of the ketoester compound include known ones such as methyl benzoylformate and ethyl benzoylformate.

As the phosphine oxide compound, known compounds can be included. For example, 6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide Can be mentioned.

Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-,1-(0-acetyloxime), NCI-831, NCI-930 (manufactured by ADEKA Corporation), OXE-03, OXE-04 (manufactured by BASF Corporation), etc. It will be done.

Among these, from the viewpoint of sensitivity, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime), 2-octanedione, 1 -[4-(phenylthio)-2-(O-benzoyloxime)], NCI-831, NCI-930, OXE-03, and OXE-04 are preferred.

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

Other specific examples of component (C) include known ones such as triphenylphosphine, carbon tetrabromide, and tribromophenyl sulfone.

Regarding the content of component (C), when the sum of components (A) and (B) is 100 parts by mass, a content of 0.5 parts by mass or more and 20 parts by mass or less is sufficient for obtaining sufficient sensitivity and heat resistance. This is preferable because the amount of outgassing during curing can be suppressed. Among these, 1.0 parts by mass or more and 10 parts by mass or less is more preferable.

A sensitizer may be included for the purpose of enhancing the function of component (C). By containing a sensitizer, it becomes possible to improve the sensitivity and adjust the sensitive wavelength. As the sensitizer, known ones can be included. Bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine and these Examples include, but are not limited to, derivatives of.

The photosensitive resin composition may contain a crosslinking agent. The crosslinking agent is a compound having a functional group that can be crosslinked by heat, and specific examples of the functional group include an epoxy group, an oxetane group, and a methylol group.

Known epoxy compounds can be included. For example, Epolite (registered trademark) 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 (all product names, manufactured by Kyoeisha Chemical Co., Ltd.) ), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L (trade names, manufactured by Nagase ChemteX Co., Ltd.), Epicote 828, Epicote 1002, Epicote 1750, Epicort 1007, YX8100-BH30, E1256, E4250, E4275 (all product names, manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon EXA-9583, Epiclon N695, HP4032, HP7200 (all product names, manufactured by Dainippon Ink and Chemicals Co., Ltd.) (manufactured by Nissan Chemical Industries, Ltd.), VG3101 (product name, manufactured by Mitsui Chemicals, Inc.), Tepic S, Tepic G, Tepic P (product names, manufactured by Nissan Chemical Industries, Ltd.), Epotote YH-434L (product name, Toto (manufactured by Kasei Co., Ltd.), GAN, GOT, EPPN502H, NC3000 or NC6000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

It may contain known oxetane compounds. For example, OXT-101, OXT-121, OXT-212, OXT-221 (trade names manufactured by Toagosei Co., Ltd.), etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA, etanacol OXIPA (trade names) (manufactured by Ube Industries, Ltd.) or oxetanated phenol novolak.

Known methylol compounds can be included. 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, TriML-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 (all product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC Examples include MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.).

The photosensitive resin composition may contain a solvent. As a solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - Polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyric acid amide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more types of these may be contained.

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

The photosensitive resin composition may contain a known antioxidant, surfactant, and adhesion improver.

The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.

The cured product is obtained by applying the photosensitive resin composition to a base material and drying it to evaporate the solvent. Thereafter, after carrying out an exposure and post-exposure baking process as necessary, it can be obtained by curing by applying a temperature of 150° C. to 350° C. This heat treatment is carried out either by selecting a certain temperature and increasing the temperature stepwise, or by selecting a certain temperature range and increasing the temperature continuously for 5 minutes to 5 hours. For example, heat treatment is performed at 130° C. and 200° C. for 30 minutes each. The lower limit of the curing conditions in the present invention is preferably 170° C. or higher, and more preferably 180° C. or higher to allow curing to proceed sufficiently. Further, there is no particular restriction on the upper limit of the curing conditions, but from the viewpoint of suppressing film shrinkage and stress, it is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 230°C or lower.

When patterning the cured product, the resin composition may be patterned by a known method including a coating process, a drying process, an exposure process, a development process, a post-exposure baking process, a heat curing process, and the like.

The electronic component of the present invention has the cured product of the present invention.

A cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or a protective film constituting electronic components.

Here, examples of electronic components include active components including semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, and passive components such as resistors, capacitors, and inductors. Further, an electronic component using a semiconductor is also referred to as a semiconductor device or a semiconductor package.

Specific examples of cured products in electronic components include passivation films for semiconductors, surface protection films for semiconductor elements, TFTs (Thin Film Transistors), etc., and interlayer insulation between rewirings in multilayer wiring for high-density packaging of 2 to 10 layers. It is suitably used for applications such as an interlayer insulating film such as a film, an insulating film for a touch panel display, a protective film, an insulating layer for an organic electroluminescent device, etc., but is not limited thereto and can take various structures.

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

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

(1) Pattern processability After spin-coating varnish on a silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), the varnish was coated on a silicon wafer using a hot plate (SCW-636 manufactured by Dainippon Screen Manufacturing Co., Ltd.) for 120 minutes. Prebaking was performed at ℃ for 3 minutes to produce a prebaked film having a thickness of 11 μm. A parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) was used to form a 30 μm 1:1 line and space pattern on the obtained prebaked film using an ultra-high pressure mercury lamp as a light source. Exposure was performed at 500 mJ/cm ² (g, h, i-ray mixture) through a contact through a mask.

Thereafter, post-exposure baking was performed at 120° C. for 1 minute, and development was performed using a coating and developing device MARK-7. Paddle development was performed with a 2.38% by mass aqueous solution of tetramethylammonium (TMAH), and then rinsed with pure water.

60 seconds after the start of development, a 30 μm 1:1 line and space space in the patterned area was observed. If any residue remained in the space, the space was observed after additional development for 60 seconds, and 60 seconds of additional development and observation were repeated until the residue was completely removed. Rinsing was performed for 20 seconds after each additional development. When the development start time is 0 seconds, A is the one that can be processed in 60 seconds, B is that the total development time is 120 seconds, C is that is the one that can be processed in 180 seconds, and C is the one that can be processed in 240 seconds or more. The developability was evaluated as D for those that could be processed, and E for those that could not be processed even after 240 seconds or more of development.

The film thickness was measured after development, and the remaining film ratio was calculated by dividing the post-development film thickness of the exposed area by the pre-bake film thickness, assuming that the pre-bake film thickness was 100. Sensitivity was evaluated as A when the remaining film rate was 80% or more, B when it was 65% or more and less than 80%, C when it was 50% or more and less than 65%, and D when it was less than 50%. The film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. with a refractive index of 1.629. The same applies to the film thickness described below.

(2) Evaluation of dielectric properties Varnish was applied and prebaked on a 6-inch silicon wafer using a spin coating method using a coating and developing device Mark-7 so that the film thickness after prebaking at 120°C for 3 minutes was 11 μm. After that, the entire surface of the PLA was exposed to 500 mJ/cm ² , and an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) was used to expose the entire surface to 220 mJ/cm at 3.5°C/min at an oxygen concentration of 20 ppm or less. The temperature was raised to .degree. C., and heat treatment was performed at 220.degree. C. for 1 hour. When the temperature reached 50° C. or below, the silicon wafer was taken out and immersed in 45% by mass hydrofluoric acid for 5 minutes to peel off the cured resin composition from the wafer. This film was cut into strips with a width of 3 cm and a length of 10 cm, and the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured at a room temperature of 23.0°C and a humidity of 45.0% RH using the perturbation method cavity resonator method in accordance with ASTM D2520. It was measured. The dielectric properties were evaluated in five stages as shown in Table 1 below.

(3) Evaluation of heat resistance A self-supporting film of the cured product was prepared in the same manner as in the above "(2) Evaluation of dielectric properties", and the cured product obtained by this method was diluted to a size of 3.0 cm x 1.5 cm. It was cut out with a single blade and measured by increasing the temperature from 25°C to 400°C at a rate of 10°C/min under nitrogen flow at 80 mL/min using a thermomechanical analyzer (TMA/SS6100, manufactured by Seiko Instruments). The evaluation criteria were as follows, and the evaluation was performed in three stages. The higher the glass transition point, the higher the heat resistance of the cured product.
A: Glass transition point value is 180°C or more B: Glass transition point value is 150°C or more and less than 180°C C: Glass transition point value is less than 150°C (4) Crack test Perform crack resistance evaluation on copper wiring. For this purpose, we prepared the following evaluation board. Cylindrical copper interconnections having a thickness of 5 μm and a diameter of 250 μm were formed on an 8-inch silicon wafer at equal intervals so that the distance between the centers of the copper interconnects was 500 μm. This was used as an evaluation board.

The varnish was applied onto the above evaluation substrate using a spin coating method using a coating and developing device Mark-7 so that the film thickness after heat treatment at 120° C. for 3 minutes was 11 μm, and prebaking was performed to prepare a prebaked film. .

The obtained prebaked film was exposed to light at an exposure dose of 500 mJ/cm ² using a PLA mask capable of forming a circular opening pattern of 150 μm on a cylindrical copper wiring. Thereafter, post-exposure baking was performed at 120° C. for 1 minute, and development was performed using a coating and developing device MARK-7. It was developed using a 2.38% by mass aqueous solution of tetramethylammonium (TMAH) until a circular pattern was opened, then rinsed with pure water, and dried by shaking it off.

Thereafter, the patterned film was heated from 50°C to 220°C at a rate of 3.5°C/min under a nitrogen stream with an oxygen concentration of 20 ppm or less using an inert oven CLH-21CD-S, and heat-treated at 220°C for 1 hour. The pattern-forming film was cured to obtain a cured product. When the temperature became 50° C. or lower, the evaluation board (hereinafter referred to as a sample) was taken out.

Next, the sample was placed in a thermal cycle tester (conditions: -65°C to 150°C) and subjected to 200 cycles. Thereafter, the sample was taken out and the presence or absence of cracks in the cured product was observed using an optical microscope. A total of 10 locations were observed, two at the center of the board and two at each of the four edges of the board. Those with zero cracks were considered to be extremely good; A, those with 1 to 2 cracks were considered good; B, and those with 3 to 2 cracks. Those with 4 cracks were rated as slightly poor and rated as C, and those with 5 or more cracks were rated as poor and rated as D. The smaller the number of cracks, the better the crack resistance.
(5) Storage stability After measuring the viscosity of the varnish using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.), it was placed in a sealed container, and the container was left in a constant temperature bath at 23.0°C for 14 days. . Thereafter, the viscosity was measured again and the rate of change was calculated. If the viscosity change rate obtained from the calculation result is less than 5%, it is considered to be very good.A is considered to be very good.If it is 5% or more and less than 10%, it is considered to be good.If it is 10% or more and less than 15%, it is considered to be normal.C. % or more was considered unstable and evaluated as D.

Below, abbreviations of compounds used in synthesis examples and examples are described.
Priamine 1075: Dimer diamine compound (trade name, manufactured by Croda Japan Co., Ltd.) (average amine value: 205)
Karenz AOI: 2-acryloyloxyethyl isocyanate (trade name, manufactured by Showa Denko K.K.)
Polyflow 77: Acrylic surfactant (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
ABPS: bis(3-amino-4-hydroxyphenyl) sulfone BAHF: 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane BPE: bis(4-chlorocarbonylphenyl) ether DCP-A: di Cyclopentadiene dimethacrylate (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
DAE: 4,4'-diaminodiphenyl ether DFA: Dimethylformamide dimethyl acetal EL: Ethyl lactate HxOH: 1-hexanol IRGANOX3114: Hindered phenol antioxidant (trade name, manufactured by BASF Corporation)
MOM: 4-[1,1-bis[4-hydroxy-3,5-bis(methoxymethyl)phenyl]ethyl]-2,6-bis(methoxymethyl)phenol NA: 5-norbornene-2,3-dicarvone Acid anhydride NCI-831: Photopolymerization initiator (trade name, manufactured by ADEKA Co., Ltd.)
NMP: N-methyl-2-pyrrolidone ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BMI-689: Polyfunctional monomer with the following structure having a maleimide group (trade name, Designer Molcules Inc.) made)

U-847: Polyfunctional monomer with the following structure having a urethane group (trade name, manufactured by Designer Molcules Inc.)

[Synthesis Example 1 Synthesis of polyfunctional monomer (M-1)]
Under a stream of dry nitrogen, 28.22 g (0.20 mol) of Karenz AOI and 28.22 g of toluene were placed in a three-necked flask and stirred. Furthermore, a solution of 53.50 g (0.10 mol) of preamine 1075 dissolved in 53.50 g of toluene was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature for 12 hours, and then toluene was removed using an evaporator to obtain a polyfunctional monomer (M-1). A nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., JNM-ECZ400R) was used to identify the structure of the obtained polyfunctional monomer. The results are shown below.
¹ H-NMR (DMSO): 6.4 (d, 2H), 6.0-6.2 (m, 6H), 5.8 (d, 2H), 4.3 (m, 4H), 3. 4 (m, 4H), 3.1 (m, 4H), 1.2-1.5 (m, 60H), 0.9 (t, 6H).

[Synthesis Example 2 Synthesis of polyimide (P-1)]
Under a stream of dry nitrogen, 18.31 g (0.050 mol) of BAHF and 14.02 g (0.050 mol) of ABPS were dissolved in 200.0 g of NMP in a three-necked flask. A solution of 31.02 g (0.10 mol) of ODPA dissolved in 50.00 g of NMP was added thereto, and the mixture was stirred at 50° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while water was azeotroped with the xylene. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (P-1).

[Synthesis Example 3 Synthesis of polyimide (P-2)]
Under a stream of dry nitrogen, 18.31 g (0.050 mol) of BAHF, 14.02 g (0.050 mol) of ABPS, and 2.96 g (0.020 mol) of phthalic anhydride as an end-capping agent were dissolved in 200.0 g of NMP in a three-necked flask. Ta. A solution of 27.92 g (0.090 mol) of ODPA dissolved in 40.00 g of NMP was added thereto, and the mixture was stirred at 50° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while water was azeotroped with the xylene. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (P-2).

[Synthesis Example 4 Synthesis of polyimide (P-3)]
Under a stream of dry nitrogen, 14.65 g (0.040 mol) of BAHF, 14.02 g (0.050 mol) of ABPS, and 1.86 g (0.020 mol) of aniline as an end-blocking agent were dissolved in 200.0 g of NMP in a three-necked flask. A solution of 31.02 g (0.10 mol) of ODPA dissolved in 40.00 g of NMP was added thereto, and the mixture was stirred at 50° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while water was azeotroped with the xylene. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (P-3).

[Synthesis Example 5 Synthesis of polyimide (P-4)]
Under a stream of dry nitrogen, 18.31 g (0.050 mol) of BAHF and 14.02 g (0.050 mol) of ABPS were dissolved in 200.0 g of NMP in a three-necked flask. A solution of 27.92 g (0.090 mol) of ODPA dissolved in 40.00 g of NMP was added thereto, and the mixture was stirred at 50° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while water was azeotroped with the xylene. After the reaction was completed, a solution of 1.57 g (0.020 mol) of acetyl chloride dissolved in 10 g of NMP was added as an end-capping agent, and the mixture was stirred at 20°C for 2 hours and then at 50°C for 2 hours. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (P-4).

[Synthesis Example 6 Synthesis of polyimide (P-5)]
Polyimide (P-5) was obtained in the same manner as Synthesis Example 3 except that 2.96 g (0.020 mol) of phthalic anhydride was replaced with 3.28 g (0.020 mol) of NA.

[Synthesis Example 7 Synthesis of polyimide (P-6)]
Polyimide (P-6) was obtained in the same manner as in Synthesis Example 4, except that 1.86 g (0.020 mol) of aniline was replaced with 2.38 g (0.020 mol) of 4-aminostyrene.

[Synthesis Example 8 Synthesis of polyimide (P-7)]
Polyimide (P-7) was obtained in the same manner as in Synthesis Example 5, except that 1.57 g (0.020 mol) of acetyl chloride was replaced with 3.33 g (0.020 mol) of cinnamoyl chloride.

[Synthesis Example 9 Synthesis of polyimide (P-8)]
Performed in the same manner as Synthesis Example 6 except that 18.31 g (0.050 mol) of BAHF and 14.02 g (0.050 mol) of ABPS were replaced with 9.16 g (0.025 mol) of BAHF and 15.02 g (0.075 mol) of DAE. Polyimide (P-8) was obtained.

[Synthesis Example 10 Synthesis of polyimide (P-9)]
Except that BAHF18.31g (0.050mol) and ABPS14.02g (0.050mol) were replaced with BAHF18.31g (0.050mol), ABPS9.81g (0.035mol), and DAE3.00g (0.015mol). The same procedure as in Synthesis Example 6 was carried out to obtain polyimide (P-9).

[Synthesis Example 11 Synthesis of polyimide (P-10)]
Performed in the same manner as Synthesis Example 6 except that 18.31 g (0.050 mol) of BAHF and 14.02 g (0.050 mol) of ABPS were replaced with 12.82 g (0.035 mol) of BAHF and 13.02 g (0.065 mol) of DAE. Polyimide (P-10) was obtained.

[Synthesis Example 12 Synthesis of polyimide precursor (P-11)]
Under a stream of dry nitrogen, put 27.92 g (0.090 mol) of ODPA, 3.28 g (0.020 mol) of NA as an end sealing material into a three-necked flask, and further add 2.04 g (0.020 mol) of HxOH and 200.0 ml of NMP. was added thereto, and 2.02 g (0.020 mol) of triethylamine was added thereto at room temperature with stirring to obtain a reaction mixture. After the exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours. Next, the temperature was raised to 40°C, 7.67 g (0.020 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate was added to the reaction mixture, and the mixture was stirred for 30 minutes. did. After further stirring at room temperature for 2 hours, 18.31 g (0.050 mol) of BAHF, 5.61 g (0.020 mol) of ABPS, 6.01 g (0.030 mol) of DAE, and 50.00 g of NMP were added and stirred for 1 hour. Obtained. The resulting reaction solution was allowed to cool to room temperature and added to 3 L of water to produce a precipitate consisting of a crude polymer. This precipitate was collected by filtration, washed three times with water, washed twice with 500 mL of isopropyl alcohol, and dried under vacuum to obtain a powdery polyimide precursor (P-11). The esterification rate of the obtained polyimide precursor was 5 mol%.

[Synthesis Example 13 Synthesis of polyimide precursor (P-12)]
Synthesis except that BAHF18.31g (0.050mol) ABPS5.61g (0.020mol) and DAE6.01g (0.030mol) were replaced with BAHF12.82g (0.035mol) and DAE13.02g (0.065mol). A polyimide precursor (P-12) was obtained in the same manner as in Example 12. The esterification rate of the obtained polyimide precursor was 8 mol%.

[Synthesis Example 14 Synthesis of polyimide precursor (P-13)]
Synthesis except that BAHF18.31g (0.050mol) ABPS5.61g (0.020mol) and DAE6.01g (0.030mol) were replaced with BAHF18.31g (0.050mol) and DAE10.01g (0.050mol). A polyimide precursor (P-13) was obtained in the same manner as in Example 12. The esterification rate of the obtained polyimide precursor was 6 mol%.

[Synthesis Example 15 Synthesis of polyimide precursor (P-14)]
Under a stream of dry nitrogen, 27.92 g (0.090 mol) of ODPA and 3.28 g (0.020 mol) of NA as an end sealing material were placed in a three-necked flask, followed by 10.3 g (0.10 mol) of HxOH and 200.0 ml of NMP. was added thereto, and 10.1 g (0.10 mol) of triethylamine was added thereto while stirring at room temperature to obtain a reaction mixture. After the exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours. Next, the temperature was raised to 40°C, 38.3 g (0.10 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate was added to the reaction mixture, and the mixture was stirred for 30 minutes. did. After further stirring at room temperature for 2 hours, 18.31 g (0.050 mol) of BAHF, 10.01 g (0.050 mol) of DAE, and 50.00 g of NMP were added and stirred for 1 hour to obtain a reaction solution. The resulting reaction solution was allowed to cool to room temperature and added to 3 L of water to produce a precipitate consisting of a crude polymer. This precipitate was collected by filtration, washed three times with water, washed twice with 500 mL of isopropyl alcohol, and dried under vacuum to obtain a powdery polyimide precursor (P-14). The esterification rate of the obtained polyimide precursor was 47 mol%.

[Synthesis Example 16 Synthesis of polyimide precursor (P-15)]
10.3 g (0.10 mol) of HxOH, 10.1 g (0.10 mol) of triethylamine, 38.3 g (0.10 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, 3.07 g (0.030 mol) of HxOH, 3.04 g (0.030 mol) of triethylamine, and 11.5 g (0.030 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, respectively. A polyimide precursor (P-15) was obtained in the same manner as Synthesis Example 15 except for the following changes. The esterification rate of the obtained polyimide precursor was 13 mol%.

[Synthesis Example 17 Synthesis of polyimide precursor (P-16)]
10.3 g (0.10 mol) of HxOH, 10.1 g (0.10 mol) of triethylamine, 38.3 g (0.10 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, 8.17 g (0.080 mol) of HxOH, 8.10 g (0.080 mol) of triethylamine, and 30.7 g (0.080 mol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, respectively. A polyimide precursor (P-16) was obtained by carrying out the same procedure as Synthesis Example 15 except for changing the procedure. The esterification rate of the obtained polyimide precursor was 36 mol%.

[Synthesis Example 18 Synthesis of polyimide precursor (P-17)]
A polyimide precursor (P-17) was obtained in the same manner as Synthesis Example 17 except that 8.17 g (0.080 mol) of HxOH was replaced with 5.93 g (0.080 mol) of 1-butanol. The esterification rate of the obtained polyimide precursor was 37 mol%.

[Synthesis Example 19 Synthesis of polyimide precursor (P-18)]
Under a stream of dry nitrogen, 18.31 g (0.050 mol) of BAHF, 10.01 g (0.050 mol) of DAE, and 3.28 g (0.020 mol) of NA as an end-blocking agent were dissolved in 200.0 g of NMP in a three-necked flask. A solution of 27.92 g (0.090 mol) of ODPA dissolved in 40.00 g of NMP was added thereto, and the mixture was stirred at 40° C. for 2 hours. Thereafter, a solution prepared by diluting 17.87 g (0.15 mol) of DFA with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, stirring was continued at 40°C for 2 hours. After the stirring was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. Further washing was performed three times with 2 L of water, and the collected polymer solids were dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (P-18). The esterification rate of the obtained polyimide precursor was 34 mol%.

[Synthesis Example 20 Synthesis of polyimide precursor (P-19)]
Under a stream of dry nitrogen, 18.31 g (0.050 mol) of BAHF and 10.01 g (0.050 mol) of DAE were dissolved in 180.0 g of NMP in a three-necked flask. A solution of 27.92 g (0.090 mol) of ODPA dissolved in 40.00 g of NMP was added thereto, and the mixture was stirred at 40° C. for 1 hour. Furthermore, a solution of 3.33 g (0.020 mol) of cinnamoyl chloride dissolved in 20.00 g of NMP was added as an end-capping agent, and the mixture was stirred at 40° C. for 1 hour. Thereafter, a solution of 17.87 g (0.15 mol) of DFA diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, stirring was continued at 40°C for 2 hours. After the stirring was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. Further, washing was performed three times with 2 L of water, and the collected polymer solids were dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (P-19). The esterification rate of the obtained polyimide precursor was 32 mol%.

[Synthesis Example 21 Synthesis of polybenzoxazole precursor (P-20)]
Under a stream of dry nitrogen, 31.14 g (0.085 mol) of BAHF and 3.00 g (0.015 mol) of DAE were dissolved in 200.0 g of NMP in a three-necked flask. A solution of 24.05 g (0.090 mol) of dodecanedioic acid dichloride dissolved in 40.00 g of NMP was added thereto, and the mixture was stirred at 20°C for 2 hours, and then at 50°C for 2 hours. Next, a solution of 3.28 g (0.020 mol) of NA dissolved in 10 g of NMP was added as an end-capping agent, and the mixture was stirred at 50° C. for 2 hours. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polybenzoxazole precursor (P-20).

[Synthesis Example 22 Synthesis of polybenzoxazole precursor (P-21)]
Synthesis Example 21 was repeated except that 24.05 g (0.090 mol) of dodecanedioic acid dichloride was replaced with 1.34 g (0.005 mol) of dodecanedioic acid dichloride and 25.89 g (0.085 mol) of BPE. An oxazole precursor (P-21) was obtained.

[Synthesis Example 23 Synthesis of polybenzoxazole precursor (P-22)]
Synthesis Example 21 was carried out in the same manner as in Synthesis Example 21 except that 24.05 g (0.090 mol) of dodecanedioic acid dichloride was replaced with 18.7 g (0.070 mol) of dodecanedioic acid dichloride and 5.90 g (0.020 mol) of BPE. An oxazole precursor (P-22) was obtained.

[Synthesis Example 24 Synthesis of polybenzoxazole precursor (P-23)]
Under a stream of dry nitrogen, 31.14 g (0.085 mol) of BAHF and 3.00 g (0.015 mol) of DAE were dissolved in 200.0 g of NMP in a three-necked flask. A solution of 18.7 g (0.070 mol) of dodecanedioic acid dichloride and 5.90 g (0.020 mol) of BPE in 40.00 g of NMP was added thereto, stirred at 20°C for 2 hours, and then stirred at 50°C for 2 hours. Stir for hours. Next, a solution of 3.33 g (0.020 mol) of cinnamoyl chloride dissolved in 10.00 g of NMP was added as an end-capping agent, and the mixture was stirred at 50° C. for 2 hours. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polybenzoxazole precursor (P-23).

[Synthesis Example 25 Synthesis of polybenzoxazole precursor (P-24)]
Synthesis Example 21 was carried out in the same manner as in Synthesis Example 21 except that 24.05 g (0.090 mol) of dodecanedioic acid dichloride was replaced with 4.01 g (0.015 mol) of dodecanedioic acid dichloride and 22.13 g (0.075 mol) of BPE. An oxazole precursor (P-24) was obtained.

[Synthesis Example 26 Synthesis of polybenzoxazole precursor (P-25)]
Synthesis Example 21 was carried out in the same manner as in Synthesis Example 21 except that 24.05 g (0.090 mol) of dodecanedioic acid dichloride was replaced with 13.36 g (0.050 mol) of dodecanedioic acid dichloride and 11.80 g (0.040 mol) of BPE. An oxazole precursor (P-25) was obtained.

[Synthesis Example 27 Synthesis of polybenzoxazole precursor (P-26)]
Synthesis example except that 18.7 g (0.070 mol) of dodecanedioic acid dichloride and 5.90 g (0.020 mol) of BPE were replaced with 13.36 g (0.050 mol) of dodecanedioic acid dichloride and 11.80 g (0.040 mol) of BPE. A polybenzoxazole precursor (P-26) was obtained in the same manner as in Example 24.

[Synthesis Example 28 Synthesis of polyimide (P-27)]
Polyimide (P-27) was obtained in the same manner as Synthesis Example 2, except that 18.31 g (0.050 mol) of BAHF and 14.02 g (0.050 mol) of ABPS were changed to 36.63 g (0.10 mol) of BAHF. Ta.

[Example 1]
Under yellow light, 5.00 g of BMI-689, 10.00 g of P-1, 0.50 g of NCI-831, 1.00 g of MOM, 0.10 g of IRGANOX3114, 0.30 g of 3-trimethoxysilyl phthalamic acid. , was dissolved in 20.00 g of NMP, 0.10 g of a 1% by mass EL solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The characteristics of the obtained varnish were measured by the above evaluation method in terms of pattern workability, dielectric constant, dielectric loss tangent, glass transition point, and crack evaluation.

[Example 2]
The same procedure as in Example 1 was carried out except that BMI-689 was replaced with U-847.

[Example 3]
The same procedure as in Example 1 was conducted except that BMI-689 was replaced with M-1.

[Example 4]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-2.

[Example 5]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-3.

[Example 6]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-4.

[Example 7]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-5.

[Example 8]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-6.

[Example 9]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-7.

[Example 10]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-8.

[Example 11]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-9.

[Example 12]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-10.

[Example 13]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-11.

[Example 14]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-12.

[Example 15]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-13.

[Example 16]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-14.

[Example 17]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-15.

[Example 18]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-16.

[Example 19]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-17.

[Example 20]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-18.

[Example 21]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-19.

[Example 22]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-20.

[Example 23]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-21.

[Example 24]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-22.

[Example 25]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-23.

[Example 26]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-24.

[Example 27]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-25.
[Example 28]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-26.

[Comparative example 1]
Under yellow light, 10.00 g of P-1, 5.00 g of DCP-A, 0.50 g of NCI-831, 1.00 g of MOM, 0.10 g of IRGANOX3114, 0.30 g of 3-trimethoxysilyl phthalamic acid, It was dissolved in 20.00 g of NMP, 0.10 g of a 1% by mass EL solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The characteristics of the obtained varnish were measured by the above evaluation method in terms of pattern processability, dielectric constant, dielectric loss tangent, glass transition point, storage stability, and crack evaluation.

[Comparative example 2]
The same procedure as in Example 1 was carried out except that P-1 was replaced with P-27.

Claims (13)

A photosensitive resin composition containing (A) a polyfunctional monomer, (B) an alkali-soluble resin, and (C) a photopolymerization initiator,
The (A) polyfunctional monomer contains a compound represented by formula (1) and/or a compound represented by formula (2),
The alkali-soluble resin (B) includes (B1) a polyimide having a structural unit represented by formula (3), (B2) a polyimide precursor having a structural unit represented by formula (4), and (B3) a polyimide precursor having a structural unit represented by formula (4). 5) Contains one or more types selected from the group consisting of polybenzoxazole precursors having the structural unit represented by and copolymers thereof,
The fluorine atom concentration in the polyimide having the structural unit represented by the formula (3) (B1) is 0.1% by mass or more and 10% by mass or less,
The fluorine atom concentration in the polyimide precursor having the structural unit represented by the formula (4) (B2) is 0.1% by mass or more and 10% by mass or less,
Photosensitive resin composition.

(In formula (1), W ¹ and W ² each independently represent a monovalent organic group having 2 to 25 carbon atoms and having a carbon-carbon double bond.In formula (1), a, b, c and d are natural numbers that each independently satisfy a+b=6 to 17 and c+d=8 to 19, and the broken line part means a carbon-carbon single bond or a carbon-carbon double bond.)

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

(In formula (3), X ¹ represents a tetravalent organic group having 2 to 100 carbon atoms, Y ¹ represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and At least one of ¹ and Y ¹ has a fluorine atom. R ⁵ represents a phenolic hydroxyl group. * represents a bonding group.)

(In formula (4), X ² represents a tetravalent organic group having 2 to 100 carbon atoms, Y ² represents a tetravalent organic group having 6 to 100 carbon atoms having one or more aromatic rings, and At least one of ² and Y ² has a fluorine atom. R ⁷ represents a phenolic hydroxyl group, and a plurality of R ⁶ each independently represent a monovalent organic group having 1 to 20 carbon atoms or a hydrogen atom. * indicates a bond (indicates the group)

(In formula (5), X ³ represents a divalent aliphatic group having 10 to 20 carbon atoms, R ⁸ represents a single bond or a divalent to hexavalent organic group having 1 to 100 carbon atoms, and R ⁹ represents (Represents a monovalent organic group having 1 to 10 carbon atoms. r represents an integer of 0 to 4. * represents a bonding group.) In the formula (1) and the formula (2), at least one of W ¹ and W ² and at least one of W ³ and W ⁴ are formula (6), formula (7), formula (8), or formula ( The photosensitive resin composition according to claim 1, which is a group represented by 9).

(In formula (6), formula (7), formula (8) and formula (9), K ¹ , K ² , K ³ , K ⁴ , L ¹ and L ² are each independently -NH-, -O -, -CH ₂ - or -S-. R ¹ and R ³ each independently represent a single bond or a divalent to hexavalent organic group having 1 to 5 carbon atoms. R ² and R ⁴ each independently represent represents a single bond or a divalent organic group consisting of 1 to 5 carbon atoms. i and j each independently represent an integer of 1 to 5. * represents a bonding point.) The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (B) has one or more types of structures represented by formula (10).

(In formula (10), W ⁵ represents a monovalent organic group having 1 to 20 carbon atoms that does not have an amino group, and W ⁶ represents a monovalent organic group having 1 to 20 carbon atoms that does not have a carboxyl group. W ⁷ represents a divalent organic group having 3 to 20 carbon atoms and does not have a carboxyl group. * ¹ represents a bond with a carbon atom, * ² represents a hydrogen atom or * ³ and * ⁴ each independently represent a bond with a nitrogen atom; * ⁵ represents a bond with a hydrogen atom, carbon atom, nitrogen atom, or oxygen atom. ) In the formula (10), W ⁵ is a monovalent organic group having 2 to 20 carbon atoms and has a polymerizable unsaturated bond and no amino group, and W ⁶ is a polymerizable unsaturated group. A monovalent organic group having 2 to 20 carbon atoms that has a bond and does not have a carboxyl group, and W ⁷ has a polymerizable unsaturated bond and does not have a carboxyl group. The photosensitive resin composition according to claim 3, which is a divalent organic group having 3 to 20 carbon atoms. The photosensitive resin composition according to claim 1 or 2, wherein the diamine residue having a phenolic hydroxyl group is in the range of 30 mol% or more and 90 mol% or less out of 100 mol% of the total diamine residues in the alkali-soluble resin (B). The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (B) contains a polyimide precursor having a structural unit represented by formula (4) (B2). A claim in which the diamine residue having a phenolic hydroxyl group is in the range of 30 mol% or more and 60 mol% or less out of 100 mol% of all diamine residues in the polyimide precursor having the structural unit represented by formula (4) (B2). 3. The photosensitive resin composition according to 1 or 2. The photosensitive resin composition according to claim 1 or 2, wherein the polyimide precursor having the structural unit represented by formula (4) (B2) has an esterification rate in a range of 10 mol% or more and 40 mol% or less. The photosensitive resin composition according to claim 1 or 2, wherein R ⁶ in the formula (4) is a monovalent organic group having 1 to 4 carbon atoms or a hydrogen atom. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (B) contains a polybenzoxazole precursor having a structural unit represented by formula (5) (B3). (B3) Among 100 mol% of all dicarboxylic acid residues in the polybenzoxazole precursor having the structural unit represented by formula (5), 10 mol% of dicarboxylic acid residues having an aliphatic group having 10 to 20 carbon atoms. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition is in a range of 50 mol% or more. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2. An electronic component comprising the cured product according to claim 12.