Photosensitive resin composition, cured film, electronic device, and electronic device manufacturing method

Abstract

This photosensitive resin composition contains an alkali-soluble resin (A), a polyether-modified polydimethylsiloxane (B), a solvent (C), and a photosensitizer (D). The polystyrene-equivalent weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) as measured by gel permeation chromatography is 1000-5000.

Description

Photosensitive resin composition, cured film, electronic device, and method for manufacturing electronic device

[0001] The present invention relates to a photosensitive resin composition, a cured film, an electronic device, and a method for producing an electronic device.

[0002] A cured film obtained by exposing a photosensitive resin composition to light is sometimes used as a permanent film constituting an electronic device. Techniques relating to such photosensitive resin compositions include, for example, those described in Patent Document 1.

[0003] Patent Document 1 aims to provide a photosensitive resin composition that has excellent chemical resistance while maintaining high sensitivity, and describes a photosensitive resin composition that includes: (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) a polymer having (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group; (2) a polymer having (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group; (B) a photoacid generator; (C) an aromatic heterocyclic compound; and (D) a solvent, wherein the aromatic heterocyclic compound (C) has a molecular weight of 1,000 or less, contains at least one nitrogen atom in the aromatic ring, and contains at least two coordinating atoms in the aromatic ring.

[0004] Japanese Patent Application Laid-Open No. 2016-189006

[0005] The present invention provides a photosensitive resin composition having improved defoaming properties.

[0006] According to the present invention, there are provided a photosensitive resin composition, a cured film, an electronic device, and a method for producing an electronic device, as shown below.

[0007] [1] A photosensitive resin composition comprising an alkali-soluble resin (A), a polyether-modified polydimethylsiloxane (B), a solvent (C), and a photosensitizer (D), wherein the polyether-modified polydimethylsiloxane (B) has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 1,000 to 5,000. [2] The photosensitive resin composition according to [1], wherein the solvent (C) comprises a solvent (C1), wherein the solvent (C1) comprises at least one solvent selected from the group consisting of γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, propylene glycol monomethyl ether, 3-methyl-2-oxazolidinone, 3-methoxy-N,N-dimethylpropanamide, and propylene glycol monomethyl ether acetate. [3] The photosensitive resin composition according to [2], wherein the content of the solvent (C1) in the solvent (C) is 50% by mass or more and 100% by mass or less, based on the total amount of the solvent (C). [4] The photosensitive resin composition according to any one of [1] to [3], wherein the polyether-modified polydimethylsiloxane (B) comprises a polyether-modified polydimethylsiloxane having a ratio (Mw / Mn) of the weight average molecular weight (Mw) relative to the polystyrene equivalent of 1 or more and 10 or less. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the polyether-modified polydimethylsiloxane (B) comprises a polyether-modified polydimethylsiloxane having a weight average molecular weight of 1,000 or more and 5,000 or less, based on the polystyrene equivalent of the maximum peak of the molecular weight distribution, measured by gel permeation chromatography. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the weight average molecular weight (Mw) of the alkali-soluble resin (A) measured by gel permeation chromatography in terms of polystyrene is 5,000 to 70,000. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the polyether-modified polydimethylsiloxane (B) is 10 ppm to 3,000 ppm with respect to the entire photosensitive resin composition.[8] The photosensitive resin composition according to any one of [1] to [7], further comprising an adhesion aid (E). [9] The photosensitive resin composition according to any one of [1] to [8], wherein the polyether-modified polydimethylsiloxane (B) comprises a polyether-modified polydimethylsiloxane represented by the following general formula (1): (In the general formula (1), m is 1 or more and 5 or less on average, p is 1 or more and 10 or less on average, and q is 0 or more and less than 1 on average. R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)

[10] The photosensitive resin composition according to [9], wherein, in the general formula (1), x is 1 or more and 50 or less on average, and y is 1 or more and 10 or less on average.

[11] The photosensitive resin composition according to [9] or

[10] , wherein, in the general formula (1), x / y is 1 or more and 5 or less.

[12] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to

[11] .

[13] An electronic device comprising the cured film according to

[12] .

[14] A method for producing an electronic device, comprising a step of forming a coating film on a substrate using the photosensitive resin composition according to any one of [1] to

[11] .

[15] The method for producing an electronic device according to

[14] , further comprising a step of cleaning the coating film on the back side of the substrate.

[0008] According to the present invention, a photosensitive resin composition having improved defoaming properties can be provided.

[0009] 1 is a diagram showing an example of an electronic device including the photosensitive resin composition of the present embodiment.

[0010] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expression "a to b" in the description of a range of values ​​means that the range is from a to b, unless otherwise specified.

[0011] The photosensitive resin composition of the present embodiment contains an alkali-soluble resin (A), a polyether-modified polydimethylsiloxane (B), a solvent (C), and a photosensitizer (D), and the polyether-modified polydimethylsiloxane (B) has a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 5,000 or less, as measured by gel permeation chromatography.

[0012] The polyether-modified polydimethylsiloxane (B) of this embodiment has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 1,000 or more, preferably 1,200 or more, more preferably 1,300 or more, and even more preferably 1,400 or more, from the viewpoint of further improving the defoaming properties and the affinity to aqueous solvents; and from the viewpoint of further improving the defoaming properties, it is 5,000 or less, preferably 4,000 or less, more preferably 3,000 or less, even more preferably 2,500 or less, and even more preferably 2,000 or less. In addition, in the polyether-modified polydimethylsiloxane (B) of the embodiment, the weight average molecular weight (Mw) in terms of polystyrene, as measured by gel permeation chromatography, is 1,000 to 5,000, preferably 1,200 to 4,000, more preferably 1,300 to 3,000, even more preferably 1,400 to 2,500, and still more preferably 1,400 to 2,000, from the viewpoint of further improving defoaming properties and affinity to aqueous solvents. Polyether-modified polydimethylsiloxanes (B) can be used singly or in combination of two or more. When two or more polyether-modified polydimethylsiloxanes (B) are used, it is sufficient that the weight average molecular weight (Mw) of one of the polyether-modified polydimethylsiloxanes (B) is within the above range, but it is preferable that the weighted average of the weight average molecular weights (Mw) of the polyether-modified polydimethylsiloxanes (B) is within the above range.

[0013] In this embodiment, the weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) can be calculated using a molecular weight distribution curve obtained by GPC (Gel Permeation Chromatography). The weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) is calculated using a polystyrene-equivalent value obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement. The GPC measurement conditions are, for example, as follows: Apparatus: Gel permeation chromatography apparatus HLC-8320GPC manufactured by Tosoh Corporation Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatogram Measurement temperature: 40°C Solvent: THF Flow rate: 0.35 mL / min Sample concentration in measurement solution: 2.0 mg / mL

[0014] Demands for cured films used in electronic devices are becoming increasingly high. For example, during the production of a cured film, bubbles generated during the production of a photosensitive resin composition can cause voids and defects in the resulting cured film, resulting in reduced productivity of the cured film and reduced reliability of the electronic device. In other words, improved defoaming properties are required for photosensitive resin compositions. Furthermore, conventional photosensitive resin compositions use fluorine-based surfactants as surfactants, which limits their use due to environmental impact. The photosensitive resin composition of this embodiment includes an alkali-soluble resin (A), a polyether-modified polydimethylsiloxane (B), a solvent (C), and a photosensitizer (D). Since the weight-average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) is within the above range, the defoaming properties of the photosensitive resin composition can be improved while reducing the amount of fluorine-based surfactant used. Although the reason for this is not clear, it is believed that when the weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) is within an appropriate range, the compatibility between the polyether-modified polydimethylsiloxane (B) and the solvent (C) is improved, and foam stability is reduced, thereby improving the defoaming properties of the photosensitive resin composition. Furthermore, the presence of a polyether-modified group makes the polyether-modified polydimethylsiloxane (B) suitably non-polar, which reduces foam stability, thereby improving the defoaming properties of the photosensitive resin composition.

[0015] Each component of the photosensitive resin composition according to this embodiment will be described below.

[0016] (Alkali-Soluble Resin (A)) The alkali-soluble resin (A) can be selected depending on the physical properties required for the resin film, such as mechanical properties and optical properties. Specific examples of the alkali-soluble resin (A) include polyamide resins, polybenzoxazole resins, polyimide resins, phenolic resins, hydroxystyrene resins, and cyclic olefin resins, and one or more of these can be used in combination. Of the above specific examples, the alkali-soluble resin (A) preferably contains one or more selected from the group consisting of polyamide resins and polybenzoxazole resins, and more preferably contains a polybenzoxazole resin. This can further improve the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition. In addition, by further improving the physical properties, such as the mechanical strength, of the cured film made of the photosensitive resin composition, the uniformity of the film thickness can be improved and the occurrence of defects can be further suppressed.

[0017] (Polyamide resin, polybenzoxazole resin) The polyamide resin preferably contains an aromatic polyamide containing an aromatic ring in the structural unit of the polyamide, and more preferably contains a structural unit represented by the following formula (PA1). This can further improve the physical properties such as mechanical strength of the cured film made of the photosensitive resin composition, thereby further improving the uniformity of the film thickness and further suppressing the occurrence of defects. In this embodiment, the aromatic ring refers to a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, or a pyrene ring; or a heteroaromatic ring such as a pyridine ring or a pyrrole ring. From the viewpoint of further improving the mechanical strength, the polyamide resin of this embodiment preferably contains a benzene ring as the aromatic ring.

[0018]

[0019] The polyamide resin containing the structural unit represented by formula (PA1) is a precursor of polybenzoxazole resin. The polyamide resin containing the structural unit represented by formula (PA1) can be dehydrated and cyclized to form a polybenzoxazole resin by, for example, heat treatment at a temperature of 150°C to 420°C for 30 minutes to 50 hours. Here, the structural unit of formula (PA1) becomes a structural unit represented by formula (PBO1) by dehydration and cyclization.

[0020] When the alkali-soluble resin (A) according to this embodiment includes a polyamide resin containing a structural unit represented by the formula (PA1), for example, the photosensitive resin composition may be subjected to the heat treatment described above to dehydrate and ring-close the polyamide resin to form a polybenzoxazole resin. That is, when a photosensitive resin composition containing a polyamide resin is subjected to the heat treatment described above, the photosensitive resin composition contains a polybenzoxazole resin. Furthermore, when the alkali-soluble resin (A) includes a polyamide resin containing a structural unit represented by the formula (PA1), the polyamide resin may be subjected to the heat treatment described above after preparing a cured film described below to dehydrate and ring-close the polybenzoxazole resin. When the polyamide resin is converted into a polybenzoxazole resin by dehydrating and ring-opening the polyamide resin, the mechanical properties and thermal properties can be further improved, and deformation of the cured film can be further suppressed.

[0021]

[0022] (Polyamide Resin, Polyimide Resin) Furthermore, as the polyamide resin, for example, one containing a structural unit represented by the following formula (PA2) may be used. A polyamide resin containing a structural unit represented by the following formula (PA2) is a precursor of a polyimide resin. A polyamide resin containing a structural unit represented by the following formula (PA2) can be converted into a polyimide resin by dehydration and ring closure, for example, by heat treatment at a temperature of 150°C or higher and 420°C or lower for 30 minutes to 50 hours. Here, the structural unit of the following formula (PA2) becomes a structural unit represented by the following formula (PI1) by dehydration and ring closure. When the alkali-soluble resin (A) according to this embodiment is a polyamide resin containing a structural unit represented by the following formula (PA2), the photosensitive resin composition may be subjected to the above heat treatment to dehydrate and ring closure, thereby converting it into a polyimide resin. That is, the heat-treated photosensitive resin composition contains a polyimide resin that is the alkali-soluble resin (A). Furthermore, when the alkali-soluble resin (A) contains a polyamide resin containing a structural unit represented by the following formula (PA2), after producing a resin film and an electronic device described below, the resin may be subjected to the above-mentioned heat treatment to dehydrate and ring-close the polyimide resin.

[0023]

[0024] In formula (PA2), R Ｂ and R Ｃ are preferably each independently an organic group having 1 to 30 carbon atoms.

[0025] In formula (PI1), R Ｂ and R Ｃ is the same as the above formula (PA2).

[0026] R in formula (PA2) and formula (PI1) Ｂ and R Ｃ is preferably an organic group having an aromatic ring. The organic group having an aromatic ring is preferably one containing a benzene ring, a naphthalene ring, or an anthracene ring, more preferably one containing a benzene ring. This can further improve the dispersibility of the alkali-soluble resin (A) and further improve the defoaming property of the photosensitive resin composition.

[0027] (Method for Producing Polyamide Resin) Polyamide resin can be polymerized, for example, as follows. First, in a polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed to polymerize polyamide. Next, in a low-molecular-weight component removal step (S2), low-molecular-weight components are removed to obtain a polyamide resin mainly composed of polyamide.

[0028] (Polymerization Step (S1)) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing the polyamide is not limited, and specific examples thereof include melt polycondensation, acid chloride method, and direct polycondensation. Note that, instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic acid dianhydride, trimellitic anhydride, dicarboxylic acid dichloride, and active ester-type dicarboxylic acid may be used. Specific examples of methods for obtaining an active ester-type dicarboxylic acid include a method in which a dicarboxylic acid is reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

[0029] The diamine monomer and dicarboxylic acid monomer used in the polymerization of the polyamide resin are described below. The diamine monomer and dicarboxylic acid monomer may each be used alone, or one or more selected from the group consisting of two or more diamine monomers and two or more dicarboxylic acid monomers may be used.

[0030] (Diamine Monomer) As the diamine monomer used in polymerization, it is preferable to use a diamine monomer containing an aromatic ring in its structure, and it is more preferable to use a diamine monomer containing a phenolic hydroxyl group in its structure. By producing a polyamide resin using such a diamine monomer as a raw material, it is possible to control the conformation of the polyamide resin and further improve the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition.

[0031] The diamine monomer containing a phenolic hydroxyl group in its structure is preferably a diamine monomer represented by the following formula (DA1). By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the molecular chains of the polyamide resin can form a denser structure. Therefore, it is believed that the molecular structure can be frozen in a coordination where the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound, thereby further improving adhesion to the substrate. For example, when a diamine monomer represented by the following formula (DA1) is used, the polyamide resin preferably contains a structural unit represented by the following formula (PA3).

[0032]

[0033] In formula (DA1), R ４ is preferably a group formed by one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. ５ ~R １０ Preferably, each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.

[0034]

[0035] In formula (PA3), R ５ ~R １０ is the same as the above formula (DA1).

[0036] R in Formula (DA1) and Formula (PA3) ４ is preferably a group formed by one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. ４ is preferably a divalent group. Here, the divalent group refers to the valence of an atom. That is, R ４ indicates that there are two bonds to other atoms.

[0037] R in Formula (DA1) and Formula (PA3) ４When contains a carbon atom, R ４ is preferably a group having 1 to 30 carbon atoms, more preferably a group having 1 to 10 carbon atoms, even more preferably a group having 1 to 5 carbon atoms, and still more preferably a group having 1 to 3 carbon atoms.

[0038] R in Formula (DA1) and Formula (PA3) ４ When contains a carbon atom, R ４ Specific examples of the alkylene group include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Specific examples of the branched alkylene group include -C(CH ３ ) ２ -, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２- and alkylethylene groups such as -. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and groups in which two or more arylene groups are bonded together. The halogen-substituted alkylene group and halogen-substituted arylene group are preferably those in which the hydrogen atoms in the above-mentioned alkylene group and arylene group are substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, respectively. Among these, those in which the hydrogen atoms are substituted with fluorine atoms are preferred.

[0039] R in Formula (DA1) and Formula (PA3) ４ If does not contain a carbon atom, then R ４ Specific examples of the group include groups consisting of oxygen atoms or sulfur atoms.

[0040] R in Formula (DA1) and Formula (PA3) ５ ~R １０ are preferably each independently hydrogen or an organic group having from 1 to 30 carbon atoms, preferably hydrogen or an organic group having from 1 to 10 carbon atoms, more preferably hydrogen or an organic group having from 1 to 5 carbon atoms, even more preferably hydrogen or an organic group having from 1 to 3 carbon atoms, and even more preferably hydrogen or an organic group having from 1 to 2 carbon atoms. This allows the aromatic rings of the polyamide resin to be closely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound to each other in a coordinated manner, freezing the molecular structure and further improving adhesion.

[0041] R in Formula (DA1) and Formula (PA3) ５ ~R １０Specific examples of the organic group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; alkenyl groups such as allyl group, pentenyl group, and vinyl group; alkynyl groups such as ethynyl group; alkylidene groups such as methylidene group and ethylidene group; aryl groups such as tolyl group, xylyl group, phenyl group, naphthyl group, and anthracenyl group; aralkyl groups such as benzyl group and phenethyl group; cycloalkyl groups such as adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group; and alkaryl groups such as tolyl group and xylyl group.

[0042] As the diamine monomer represented by formula (DA1), it is preferable to use one or more selected from the group consisting of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-methylenebis(2-amino-3,6-dimethylphenol), 4,4'-methylenebis(2-aminophenol), 1,1-bis(3-amino-4-hydroxyphenyl)ethane, and 3,3'-diamino-4,4'-dihydroxydiphenyl ether. The use of these diamine monomers allows for a dense arrangement of aromatic rings in the polyamide resin. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound to each other in a coordinated manner, freezing the molecular structure and further improving adhesion. The diamine monomers listed above can be used alone or in combination of two or more. The structural formulas of these diamine monomers are shown below.

[0043]

[0044] (Dicarboxylic Acid Monomer) As the dicarboxylic acid monomer used in the polymerization, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in its structure. As the dicarboxylic acid monomer containing an aromatic ring, it is preferable to use one represented by the following formula (DC1). By producing a polyamide resin using such a dicarboxylic acid monomer as a raw material, it is possible to control the conformation of the polyamide resin and further improve the dispersibility of the alkali-soluble resin (A) in the mixed solvent. Furthermore, the improved dispersibility of the alkali-soluble resin (A) can further improve the defoaming property of the photosensitive resin composition.

[0045]

[0046] In formula (DC1), R １１ is preferably a group formed by one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. １２ ~R １９ Preferably, each independently represents hydrogen or an organic group having 1 to 30 carbon atoms.

[0047] For example, when a dicarboxylic acid monomer represented by the above formula (DC1) is used, the polyamide resin typically contains a structural unit represented by the following formula (PA4). １１ , R １２ ~R １９ The definition of is the same as in formula (DC1) above.

[0048]

[0049] R in formula (DC1) and formula (PA4) １１ is preferably a group formed by one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a chlorine atom, a fluorine atom, and a bromine atom. １１ is preferably a divalent group. Here, the divalent group refers to the valence of an atom. That is, R １１ indicates that there are two bonds to other atoms.

[0050] R in formula (DC1) and formula (PA4) １１ When contains a carbon atom, R １１ is preferably a group having 1 to 30 carbon atoms, more preferably a group having 1 to 10 carbon atoms, even more preferably a group having 1 to 5 carbon atoms, and still more preferably a group having 1 to 3 carbon atoms.

[0051] R in formula (DC1) and formula (PA4) １１ When contains a carbon atom, R １１ Specific examples of the alkylene group include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group. Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Specific examples of the branched alkylene group include -C(CH ３ ) ２ -, -CH(CH ３ ) -, -CH(CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ３ ) -, -C(CH ３ ) (CH ２ CH ２ CH ３ ) -, -C(CH ２ CH ３ ) ２ alkylmethylene groups such as -; -CH(CH ３ ) CH ２ -, -CH(CH ３ ) CH(CH ３ ) -, -C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ ) CH ２ -, -C(CH ２ CH ３ )２ -CH ２ - and alkylethylene groups such as -. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and groups in which two or more arylene groups are bonded together. Specific examples of the halogen-substituted alkylene group and halogen-substituted arylene group that can be used include the above-mentioned alkylene group and arylene group in which a hydrogen atom is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. Among these, it is preferable to use groups in which a hydrogen atom is substituted with a fluorine atom.

[0052] R in formula (DC1) and formula (PA4) １１ If does not contain a carbon atom, then R １１ Specific examples of the group include groups consisting of oxygen atoms or sulfur atoms.

[0053] R in formula (DC1) and formula (PA4) １２ ~R １９ are preferably each independently hydrogen or an organic group having from 1 to 30 carbon atoms, more preferably hydrogen or an organic group having from 1 to 10 carbon atoms, even more preferably hydrogen or an organic group having from 1 to 5 carbon atoms, even more preferably hydrogen or an organic group having from 1 to 3 carbon atoms, and even more preferably hydrogen.

[0054] R in formula (DC1) and formula (PA4) １２ ~R １９Specific examples of the organic group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; alkenyl groups such as allyl group, pentenyl group, and vinyl group; alkynyl groups such as ethynyl group; alkylidene groups such as methylidene group and ethylidene group; aryl groups such as tolyl group, xylyl group, phenyl group, naphthyl group, and anthracenyl group; aralkyl groups such as benzyl group and phenethyl group; cycloalkyl groups such as adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group; and alkaryl groups such as tolyl group and xylyl group.

[0055] Specific examples of dicarboxylic acid monomers that can be used include diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, and 4,4'-biphenyl dicarboxylic acid. Of the specific examples listed above, diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid is preferred, and diphenyl ether 4,4'-dicarboxylic acid is even more preferred. This allows the aromatic rings of the polyamide resin to be densely arranged. Therefore, the molecules of the alkali-soluble resin (A) and the metal molecules are more strongly bound to each other in a coordinated manner, freezing the molecular structure and further improving adhesion.

[0056] It is preferable to modify the amino groups present at the terminals of the polyamide resin simultaneously with or after the polymerization step (S1). The modification can be carried out, for example, by reacting a diamine monomer or a polyamide resin with a specific acid anhydride or a specific monocarboxylic acid. Therefore, it is preferable that the polyamide resin has terminal amino groups modified with a specific acid anhydride or a specific monocarboxylic acid. The specific acid anhydride and the specific monocarboxylic acid have one or more functional groups selected from the group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. Furthermore, the specific acid anhydride and the specific monocarboxylic acid preferably contain, for example, a nitrogen atom. This can further improve the wettability of the photosensitive resin composition with metal after post-baking.

[0057] Specific examples of the specific acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, HET anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, etc. As the specific acid anhydride, one or a combination of two or more of the above specific examples can be used.

[0058] When an amino group present at the terminal of a polyamide resin is modified with a specific cyclic acid anhydride, the specific cyclic acid anhydride undergoes ring-opening. After modifying the polyamide resin, the structural unit derived from the specific cyclic acid anhydride may be ring-closed to form an imide ring. Examples of ring-closure methods include heat treatment. Specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid. The specific monocarboxylic acid may be one of the above specific examples, or a combination of two or more of them.

[0059] Alternatively, the carboxyl groups present at the terminals of the polyamide resin may be modified simultaneously with or after the polymerization step (S1). The modification can be carried out, for example, by reacting a dicarboxylic acid monomer or a polyamide resin with a specific nitrogen-containing heteroaromatic compound. Therefore, it is preferable that the polyamide resin has terminal carboxyl groups modified with a specific nitrogen-containing heteroaromatic compound. The specific nitrogen-containing heteroaromatic compound has one or more functional groups selected from the group consisting of 1-(5-1H-triazoyl)methylamino, 3-(1H-pyrazoyl)amino, 4-(1H-pyrazoyl)amino, 5-(1H-pyrazoyl)amino, 1-(3-1H-pyrazoyl)methylamino, 1-(4-1H-pyrazoyl)methylamino, 1-(5-1H-pyrazoyl)methylamino, (1H-tetrazol-5-yl)amino, 1-(1H-tetrazol-5-yl)methylamino, and 3-(1H-tetrazol-5-yl)benzamino. This increases the number of lone electron pairs in the photosensitive resin composition. Therefore, the wettability of the photosensitive resin composition with metals after pre-baking and post-baking can be further improved. Specific examples of the specific nitrogen-containing heteroaromatic compound include 5-aminotetrazole.

[0060] (Low-Molecular-Weight Component Removal Step (S2)) Following the polymerization step (S1), it is preferable to carry out the low-molecular-weight component removal step (S2) to remove the low-molecular-weight components. Specifically, the organic layer containing the mixture of the low-molecular-weight components and the polyamide resin is concentrated by filtration or the like, and then re-dissolved in an organic solvent such as water / isopropanol. This allows the precipitate to be filtered off, yielding a polyamide resin from which the low-molecular-weight components have been removed.

[0061] For polyamide resins, it is preferable to prepare a photosensitive resin composition in the form of a varnish without undergoing a process of completely evaporating the solvent and drying the polyamide resin after the low-molecular-weight component removal process. This can further prevent the dispersibility of the alkali-soluble resin (A) from decreasing due to interactions between the polyamide resin molecules resulting from amide bonds. Therefore, the defoaming properties of the photosensitive resin composition can be further improved.

[0062] (Phenol Resin) Specific examples of the phenol resin include novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac resin, and phenol-biphenyl novolac resin; reaction products of phenol compounds with aldehyde compounds such as novolac-type phenol resin, resol-type phenol resin, and cresol novolac resin; and reaction products of phenol compounds with dimethanol compounds such as phenol aralkyl resin. The phenol resin may contain one or more of the above specific examples.

[0063] The phenolic compound used in the reaction product of the phenolic compound and the aldehyde compound or the reaction product of the phenolic compound and the dimethanol compound is not limited. Specific examples of such phenolic compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; alkylphenols such as isopropylphenol, butylphenol, and p-tert-butylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, and phloroglucinol; and biphenyl phenols such as 4,4'-biphenol. One or more of the above specific examples can be used as the phenolic compound.

[0064] The aldehyde compound used in the reaction product of the phenol compound and the aldehyde compound is not limited as long as it is a compound having an aldehyde group. Specific examples of such aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salicylaldehyde. One or more of the above specific examples can be used as the aldehyde compound.

[0065] The dimethanol compound used in the reaction product of the phenol compound and the dimethanol compound is not limited. Specific examples of such dimethanol compounds include dimethanol compounds such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3,3'-biphenyldimethanol, 2,6-naphthalenedimethanol, and 2,6-bis(hydroxymethyl)-p-cresol; and bis(alkoxymethyl) compounds such as 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, and methyl 2,6-naphthalenedicarboxylate. Examples of the dimethanol compound include bis(halogenoalkyl) compounds such as 1,4-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 3,4'-bis(chloromethyl)biphenyl, 3,3'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 3,4'-bis(bromomethyl)biphenyl, and 3,3'-bis(bromomethyl)biphenyl, and biphenyl aralkyl compounds such as 4,4'-bis(methoxymethyl)biphenyl and 4,4'-bis(methoxymethyl)biphenyl. Of the above specific examples, one or more of the dimethanol compounds can be used.

[0066] (Hydroxystyrene Resin) The hydroxystyrene resin is not limited, and specifically, a polymerization reaction product or copolymerization reaction product obtained by polymerizing or copolymerizing one or more selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene, and styrene derivatives can be used. Specific examples of the hydroxystyrene derivative and styrene derivative include those in which a hydrogen atom in the aromatic ring of hydroxystyrene or styrene is substituted with a monovalent organic group. Examples of the monovalent organic group substituting the hydrogen atom include alkyl groups such as methyl, ethyl, and n-propyl; alkenyl groups such as allyl and vinyl; alkynyl groups such as ethynyl; alkylidene groups such as methylidene and ethylidene; cycloalkyl groups such as cyclopropyl; and heterocyclic groups such as epoxy and oxetanyl groups.

[0067] (Cyclic Olefin Resin) The cyclic olefin resin is not limited, and specifically, a polymerization reaction product or copolymerization reaction product obtained by polymerizing or copolymerizing one or more types selected from the group consisting of norbornene and norbornene derivatives can be used. Specific examples of the norbornene derivatives include norbornadiene, bicyclo[2.2.1]-hept-2-ene (trivial name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride.

[0068] The lower limit of the content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, based on 100 parts by mass of the total solids content of the photosensitive resin composition. This further improves the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition, and further improves the defoaming properties of the photosensitive resin composition. Furthermore, the upper limit of the content of the alkali-soluble resin (A) in the photosensitive resin composition is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less, based on 100 parts by mass of the total solids content of the photosensitive resin composition. The total solids content of the photosensitive resin composition refers to the sum of the components contained in the photosensitive resin composition excluding the solvent.

[0069] From the viewpoint of further improving the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition, the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 5,000 or more, more preferably 6,000 or more, even more preferably 7,000 or more, and is preferably 70,000 or less, more preferably 65,000 or less, even more preferably 60,000 or less. From the viewpoint of further improving the dispersibility of the alkali-soluble resin (A) in the photosensitive resin composition, the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 5,000 or more and 70,000 or less, more preferably 6,000 or more and 65,000 or less, even more preferably 7,000 or more and 60,000 or less.

[0070] (Polyether-Modified Polydimethylsiloxane (B)) The polyether-modified polydimethylsiloxane (B) of this embodiment preferably contains a polyether-modified polydimethylsiloxane represented by the following general formula (1). This can further improve the defoaming properties when producing a photosensitive resin composition. Furthermore, the polyether-modified polydimethylsiloxane (B) represented by the following general formula (1) has a helical structure in the polydimethylsiloxane chain that is the main chain, and dimethyl groups and polyether-modifying groups that are side chains are arranged on the surface side of the helical structure, which has the advantage that the properties of the polyether-modified polydimethylsiloxane (B) can be further controlled by the structure of the side chains.

[0071]

[0072] In general formula (1), m preferably has an average value of 1 or more and 5 or less, p preferably has an average value of 1 or more and 10 or less, and q preferably has an average value of 0 or more and less than 1. R preferably represents hydrogen or an alkyl group having 1 to 5 carbon atoms.

[0073] In the polyether-modified polydimethylsiloxane (B), x in the general formula (1) is preferably 1 or more, more preferably 2 or more, and preferably 50 or less, more preferably 40 or less, on average. In the polyether-modified polydimethylsiloxane (B), x in the general formula (1) is preferably 1 or more and 50 or less, more preferably 2 or more and 40 or less. In the general formula (1), y is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less, on average. In the general formula (1), y is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less. In the general formula (1), the ratio of x to y (x / y) is preferably 1 or more, more preferably 1.2 or more, and preferably 5 or less, more preferably 4 or less. In the general formula (1), the ratio of x to y (x / y) is preferably 1 or more and 5 or less, more preferably 1.2 or more and 4 or less. When x, representing a dimethyl group, in general formula (1), is within the above range, the surface tension of the entire photosensitive resin composition can be appropriately reduced. Furthermore, when x / y is within the above range, the compatibility between the polyether-modified polydimethylsiloxane (B), the alkali-soluble resin (A), the solvent (C), and the photosensitizer (D) is improved. Furthermore, the more polar (hydrophilic) the polyether-modified group, the more stabilized the foam and the lower the defoaming properties. Conversely, the less polar (hydrophobic) the polyether-modified group, the lower the foam stability and the better the defoaming properties. When m, p, and q in general formula (1) are equal to or greater than the above lower limits, the side chain of the polyether-modified polydimethylsiloxane (B) becomes appropriately nonpolar (hydrophobic), which reduces foam stability and improves defoaming properties. Furthermore, when m, p, and q in general formula (1) are equal to or less than the above upper limit values, the compatibility of the polyether-modified polydimethylsiloxane (B) with the solvent (C), particularly γ-butyrolactone described below, is improved, and the defoaming properties are further improved.

[0074] In the polyether-modified polydimethylsiloxane (B), in general formula (1), m is preferably 1 or more, more preferably 2 or more, and preferably 5 or less, more preferably 4 or less, on average. In the polyether-modified polydimethylsiloxane (B), in general formula (1), m is preferably 1 or more and 5 or less, more preferably 2 or more and 4 or less. p is preferably 1 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, and preferably 10 or less, more preferably 9 or less, on average. p is preferably 1 or more and 10 or less, more preferably 3 or more and 10 or less, even more preferably 4 or more and 9 or less, even more preferably 5 or more and 9 or less, on average. q is preferably 0 or more and less than 1. R preferably represents hydrogen or an alkyl group having 1 to 5 carbon atoms, more preferably hydrogen or a methyl group, and even more preferably hydrogen. By having m, p, and q within the above ranges, the polyether-modified polydimethylsiloxane (B) as a whole becomes suitably non-polar (hydrophobic), thereby further improving the defoaming properties of the photosensitive resin composition. At the same time, the polyether-modified polydimethylsiloxane (B) has a moderately high polarity (hydrophilicity), which allows it to be dissolved in an aqueous solvent.

[0075] The polyether-modified polydimethylsiloxane (B) can be synthesized from a polyether compound and a polydimethylsiloxane. The m, p, q, x, and y in the general formula (1) can be adjusted by adjusting the type and mixing ratio of the polyether compound and polydimethylsiloxane used. The m, p, q, x, and y in the general formula (1) can be determined from the structures of the polyether compound and polydimethylsiloxane used in the synthesis of the polyether-modified polydimethylsiloxane (B). The m, p, q, x, and y in the general formula (1) can also be identified by known polymer structure analysis techniques such as NMR, IR, pyrolysis GC-MS, TOF-SIMS, and LC-TOF / MS.

[0076] From the viewpoint of further improving the defoaming property of the photosensitive resin composition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyether-modified polydimethylsiloxane (B) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 8 or less, even more preferably 7 or less, even more preferably 6 or less, even more preferably 4 or less, and even more preferably 3 or less. From the viewpoint of further improving the defoaming property of the photosensitive resin composition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyether-modified polydimethylsiloxane (B) is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, even more preferably 1 or more and 7 or less, even more preferably 2 or more and 6 or less, even more preferably 2 or more and 4 or less, and even more preferably 2 or more and 3 or less.

[0077] The weight-average molecular weight of the maximum peak in the polystyrene-equivalent molecular weight distribution of the polyether-modified polydimethylsiloxane (B) measured by gel permeation chromatography is preferably 1,000 or more, more preferably 1,300 or more, even more preferably 1,800 or more, and preferably 5,000 or less, more preferably 4,000 or less. The weight-average molecular weight of the maximum peak in the polystyrene-equivalent molecular weight distribution of the polyether-modified polydimethylsiloxane (B) measured by gel permeation chromatography is preferably 1,000 or more and 5,000 or less, more preferably 1,300 or more and 5,000 or less, even more preferably 1,800 or more and 4,000 or less. When the weight-average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (B) is within the above range, the defoaming properties of the photosensitive resin composition are further improved. Furthermore, when the weight-average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (B) is equal to or less than the above upper limit, compatibility with γ-butyrolactone, which will be described later, is improved, and the defoaming properties of the photosensitive resin composition are further improved.

[0078] The number average molecular weight (Mn) and weight average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (B) are the same as the weight average molecular weight (Mw) of the polyether-modified polydimethylsiloxane (B) described above, measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. The weight average molecular weight of the maximum peak of the polyether-modified polydimethylsiloxane (B) can be calculated by peak separation of the chromatogram obtained by gel permeation chromatography (GPC). Peak separation software such as Eco-SEC manufactured by Tosoh Corporation can be used. The maximum peak refers to the peak at which the integrated value of the peak is greatest.

[0079] From the viewpoint of improving the defoaming properties of the photosensitive resin composition, the surface tension (mN / m) of the polyether-modified polydimethylsiloxane (B) is preferably 20 mN / m or more, more preferably 25 mN / m or more, even more preferably 27 mN / m or more, and preferably 40 mN / m or less, more preferably 35 mN / m or less, even more preferably 30 mN / m or less. The surface tension (mN / m) of the polyether-modified polydimethylsiloxane (B) is measured using a contact angle meter at 23°C in a 1% GBL solution. A DMs-401 (Kyowa Interface Science Co., Ltd.) can be used as the contact angle meter.

[0080] The density (g / mL) of the polyether-modified polydimethylsiloxane (B), measured at 20°C in accordance with ISO 2811-3:2011, is preferably 0.90 g / mL or more, more preferably 0.95 g / mL or more, and is preferably 1.15 g / mL or less, more preferably 1.10 g / mL or less, from the viewpoint of minimizing the content of low-molecular-weight components. The refractive index of the polyether-modified polydimethylsiloxane (B), measured in accordance with DIN 51423, is preferably 1.30 or more, more preferably 1.40 or more, and is preferably 1.60 or less, more preferably 1.50 or less, from the viewpoint of minimizing the content of low-molecular-weight components. The nonvolatile content of the polyether-modified polydimethylsiloxane (B), measured in accordance with ISO 3251:2019 under heating conditions of 105°C for 1 hour, is preferably 85.0% or more, more preferably 87.0% or more, and even more preferably 90.0% or more, from the viewpoint of minimizing the content of low-molecular-weight components.

[0081] The content of polyether-modified polydimethylsiloxane (B) is preferably 10 ppm or more, more preferably 50 ppm or more, even more preferably 90 ppm or more, and preferably 3000 ppm or less, more preferably 2500 ppm or less, even more preferably 2000 ppm or less, and even more preferably 1600 ppm or less, based on the entire photosensitive resin composition. The content of polyether-modified polydimethylsiloxane (B) is preferably 10 ppm or more and 3000 ppm or less, more preferably 10 ppm or more and 2500 ppm or less, even more preferably 50 ppm or more and 2000 ppm or less, and even more preferably 90 ppm or more and 1600 ppm or less, based on the entire photosensitive resin composition. The content of polyether-modified polydimethylsiloxane (B) within the above range can further improve the defoaming properties of the photosensitive resin composition.

[0082] (Solvent (C)) The solvent (C) according to this embodiment preferably includes the following solvent (C1). The solvent (C1) preferably includes at least one selected from the group consisting of γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), propylene glycol monomethyl ether (PGME), 3-methyl-2-oxazolidinone, 3-methoxy-N,N-dimethylpropanamide, and propylene glycol monomethyl ether acetate (PGMEA). From the viewpoint of further improving the defoaming properties of the photosensitive resin composition, the solvent (C1) more preferably includes one selected from the group consisting of γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), and 3-methyl-2-oxazolidinone, and even more preferably includes γ-butyrolactone. γ-Butyrolactone is compatible with the polyether-modified polydimethylsiloxane (B) described above in that it can make the surface tension of the entire photosensitive resin composition more appropriate and can make the polarity of the polyether-modified polydimethylsiloxane (B) in the photosensitive resin composition more appropriate, and therefore the defoaming properties of the photosensitive resin composition can be further improved.

[0083] The solvent (C) may contain a solvent other than the solvent (C1), such as urea-based solvents such as N,N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-dimethylpropyleneurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea; tetrahydrofurfuryl alcohol; Examples of suitable solvents include alcohol-based solvents such as hexane, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol; ketone-based solvents such as cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone; carbonate-based solvents such as ethylene carbonate and propylene carbonate; sulfone-based solvents such as dimethyl sulfoxide (DMSO) and sulfolane; ester-based solvents such as methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate; and aromatic hydrocarbon-based solvents such as mesitylene, toluene, and xylene. The solvent may be one of the above specific examples, or a combination of two or more of them.

[0084] From the viewpoint of further improving the defoaming property of the photosensitive resin composition, the content of solvent (C1) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, based on the total amount of solvent (C). From the viewpoint of further improving the defoaming property of the photosensitive resin composition, the content of solvent (C1) is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, even more preferably 70% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less.

[0085] From the viewpoint of further improving the coatability of the photosensitive resin composition, the content of the solvent (C) is preferably 40% by mass or more, more preferably 50% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, when the total amount of the photosensitive resin composition is taken as 100% by mass.

[0086] (Photosensitizer (D)) As the photosensitizer (D), a photoacid generator that generates an acid by absorbing light energy can be used. Specific examples of photoacid generators include diazoquinone compounds; diaryliodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; imidosulfonate compounds; 2,6-bis(trichloromethyl)-1,3,5-triazine compounds; and dihydropyridine compounds. Among these, the photosensitizer (D) preferably contains a photosensitive diazoquinone compound. This can further improve the sensitivity of the photosensitive resin composition. Therefore, the pattern precision and appearance can be further improved. The photoacid generator can contain one or more of the above specific examples. Furthermore, when the photosensitive resin composition is a positive-working photosensitizer (D), in addition to the above specific examples, onium salts such as triarylsulfonium salts and sulfonium borate salts can be used in combination. This can further improve the sensitivity of the photosensitive resin composition.

[0087] Examples of diazoquinone compounds are shown below using chemical formulas.

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] In each of the above diazoquinone compounds, Q is a structure represented by the following formula (a), formula (b), or formula (c), or a hydrogen atom. However, at least one of Q in each diazoquinone compound is a structure represented by the following formula (a), formula (b), or formula (c). Q of the diazoquinone compound preferably includes the following formula (a) or formula (b). This can further improve the transparency of the photosensitive resin composition. Therefore, the appearance of the photosensitive resin composition can further be improved.

[0094]

[0095] The lower limit of the content of the photosensitizer (D) in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (A). This allows the photosensitive resin composition to exhibit appropriate sensitivity. Furthermore, the upper limit of the content of the photosensitizer (D) in the photosensitive resin composition is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (A). This prevents the photosensitive resin composition from being repelled by metal materials present on the surface of the substrate of a semiconductor device.

[0096] (Adhesion Aid (E)) The photosensitive resin composition according to this embodiment may further contain an adhesion aid (E). The adhesion aid (E) preferably contains one selected from the group consisting of a triazole compound, an aminosilane, an imide compound, an epoxysilane, a (meth)acrylicsilane, and a reaction product of an epoxy compound and an aminotriazole. This can further improve the affinity between the photosensitive resin composition and the metal member.

[0097] Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4-triazole-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1 ,2,4-triazole, 1,2,4-triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carboxamide, 3,5-diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, 4-methyl-1,2,4-triazole-3-carboxamide, etc. As the triazole compound, one or a combination of two or more of the above specific examples can be used.

[0098] Specific examples of aminosilanes include condensates of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, condensates of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)methyl]-N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)methyl]-N-phenyl-3-aminopropyltriethoxy ... Examples of aminosilanes include N,N'-bis-(3-triethoxysilylpropyl)ethylenediamine, N,N'-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(methyldiethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(dimethylmethoxysilyl)propyl]ethylenediamine, N-[3-(methyldimethoxysilyl)propyl]-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]diaminopropane, N,N'-bis[3-(trimethoxysilyl)propyl]diaminohexane, and N,N'-bis[3-(trimethoxysilyl)propyl]diethylenetriamine. Of the above specific examples, one or a combination of two or more can be used as the aminosilane.

[0099] Examples of the imide compound include the following compounds, which may be used alone or in combination of two or more.

[0100]

[0101] Specific examples of epoxy silanes include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. As the epoxy silanes, one or a combination of two or more of the above specific examples can be used.

[0102] Specific examples of the (meth)acrylic silane include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc. As the (meth)acrylic silane, one or a combination of two or more of the above specific examples can be used.

[0103] Examples of the epoxy compound and aminotriazole used in the reaction product of an epoxy compound and an aminotriazole include the following. The epoxy compound is not limited as long as it contains an epoxy group, and examples include epoxy group-containing compounds such as bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, and phenol novolac resin epoxy resin. Examples of the aminotriazole include 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole.

[0104] The content of the adhesion aid (E) in the photosensitive resin composition is preferably 0 parts by mass or more, more preferably 1.0 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 3.0 parts by mass or more, and preferably 15 parts by mass or less, more preferably 13 parts by mass or less, even more preferably 12 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (A). When the content of the adhesion aid (E) is within the above range, the dispersibility of the adhesion aid (E) in the photosensitive resin composition is improved, and the adhesion of the photosensitive resin composition to the adherend can be further improved. This can further prevent foreign matter from being mixed in between the resin film and the adherend.

[0105] In the photosensitive resin composition according to this embodiment, the total content of the alkali-soluble resin (A), the polyether-modified polydimethylsiloxane (B), the solvent (C), and the photosensitizer (D) is, from the viewpoint of further improving the defoaming properties of the photosensitive resin composition and further improving the coatability of the photosensitive resin composition, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and still more preferably 90% by mass or more, when the entire photosensitive resin composition is taken as 100% by mass, and may be, for example, 100% by mass or less, or 99% by mass or less.

[0106] In the photosensitive resin composition according to this embodiment, the total content of the alkali-soluble resin (A) and the polyether-modified polydimethylsiloxane (B) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, when the entire photosensitive resin composition is taken as 100% by mass, from the viewpoint of further improving the defoaming properties of the photosensitive resin composition and further improving the balance of mechanical properties and coatability of the photosensitive resin composition.

[0107] The photosensitive resin composition according to this embodiment may further contain additives such as a thermal crosslinking agent, an antioxidant, a dissolution promoter, a filler, and a sensitizer.

[0108] (Thermal Crosslinking Agent) The photosensitive resin composition according to this embodiment may further contain a thermal crosslinking agent. This can further improve the mechanical properties of the cured product of the photosensitive resin composition. Examples of the thermal crosslinking agent include compounds having a methylol group; phenols; compounds having an alkoxymethyl group; methylol melamine compounds; alkoxy melamine compounds; alkoxymethyl glycoluril compounds; methylol urea compounds; cyano compounds; isocyanate compounds; epoxy group-containing compounds; maleimide compounds; and xylene derivatives. As the thermal crosslinking agent, one or a combination of two or more of the above specific examples can be used.

[0109] (Antioxidant) The photosensitive resin composition according to this embodiment may further contain an antioxidant. As the antioxidant, at least one selected from a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be used. The antioxidant can further suppress oxidation of the resin film formed from the photosensitive resin composition.

[0110] (Dissolution promoter) The photosensitive resin composition according to this embodiment may further contain a dissolution promoter. The dissolution promoter is a component that can improve the solubility of the exposed portion of the coating film formed using the photosensitive resin composition in a developer and reduce scumming during patterning. As such a dissolution promoter, a compound having a phenolic hydroxyl group is preferred.

[0111] When the alkali-soluble resin (A) contains a polybenzoxazole resin having an aromatic ring or a polyimide resin having an aromatic ring, the dissolution promoter preferably contains one having a biphenol skeleton or a bisphenol A skeleton, which allows the skeleton of the alkali-soluble resin (A) to interact with the dissolution promoter, thereby further improving the dispersibility of the alkali-soluble resin (A).

[0112] (Filler) The photosensitive resin composition according to this embodiment may further contain a filler. As the filler, an appropriate filler can be selected depending on the mechanical properties and thermal properties required for the resin film formed from the photosensitive resin composition, and specific examples thereof include inorganic fillers and organic fillers. Examples of inorganic fillers include silica; metal compounds; talc; clay; mica; glass fiber; and the like. Examples of organic fillers include organosilicon powder and polyethylene powder. As the filler, one or a combination of two or more of the above may be used.

[0113] (Preparation of Photosensitive Resin Composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition. For example, the photosensitive resin composition can be prepared by mixing and dissolving the alkali-soluble resin (A), the polyether-modified polydimethylsiloxane (B), and the photosensitizer (D) in the solvent (C). This allows the photosensitive resin composition to be obtained as a varnish.

[0114] (Cured Film) The photosensitive resin composition of the present embodiment is used to form a cured film for a semiconductor device such as a wafer level package or a panel level package.

[0115] The cured film is obtained by, for example, applying a photosensitive resin composition, prebaking, exposing, and developing the composition, patterning the composition into a desired shape, and then curing the composition by postbaking. The cured film can be used as a buffer coat film (protective film), an interlayer film, a dam material, or the like for electronic devices. In particular, the cured film can be suitably used as a buffer coat film.

[0116] In the process for producing the cured film, the step of applying the photosensitive resin composition is preferably performed by, for example, spin coating, which allows a more uniform resin film to be formed on the substrate.

[0117] The thickness of the cured film is not particularly limited, but is, for example, 2 μm to 30 μm, preferably 5 μm to 20 μm. After coating the photosensitive resin composition, various methods can be used to remove the solvent (e.g., heating). However, when used in panel-level packaging, it is preferable to apply reduced-pressure drying, considering the relatively large area. That is, it is preferable to dry the panel coated with the photosensitive resin composition under a reduced-pressure environment (e.g., under an environment of 30 Pa or less).

[0118] When pre-baking is performed, the conditions are, for example, 70 to 160°C and about 5 seconds to 30 minutes. For exposure, electromagnetic waves of various wavelengths or particle beams can be used. For example, ultraviolet rays such as g-rays and i-rays, visible light, lasers, X-rays, electron beams, etc. are used. Ultraviolet rays such as g-rays or i-rays are preferred. The exposure dose is set appropriately depending on the sensitivity of the photosensitive resin composition, and is, for example, 30 to 3000 mJ / cm. ２ The exposure is usually carried out using an appropriate mask pattern. Various developers can be used for development. Examples include alkaline developers such as alkali metal carbonates, alkali metal hydroxides, and tetramethylammonium hydroxide, and organic developers such as dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl acetate. Among these, alkaline developers are preferred, and aqueous solutions of tetramethylammonium hydroxide are particularly preferred. Methods for supplying the developer include spraying, puddling, and immersion. In terms of processing large-area panels, the spraying method is preferred. The post-baking conditions (curing conditions) are not particularly limited, but are, for example, at a temperature of 80°C to 450°C for 30 minutes to 300 minutes.

[0119] (Electronic Device) Next, an example of an electronic device 100 containing the photosensitive resin composition of this embodiment will be described. The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, a semiconductor package is obtained by mounting the electronic device 100 on a wiring substrate via bumps 52. The electronic device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer includes an interlayer insulating film 30 and a top-layer wiring 34 provided on the interlayer insulating film 30. The top-layer wiring 34 is made of, for example, Al. A passivation film 32 is provided on the interlayer insulating film 30 and the top-layer wiring 34. An opening is provided in a portion of the passivation film 32, exposing the top-layer wiring 34.

[0120] A redistribution layer 40 is provided on the passivation film 32. The redistribution layer 40 includes an insulating layer 42 provided on the passivation film 32, redistribution lines 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the redistribution lines 46. An opening is formed in the insulating layer 42 to expose the top-layer wiring 34. The redistribution lines 46 are formed on the insulating layer 42 and in the openings provided in the insulating layer 42, and are electrically connected to the top-layer wiring 34. An opening is formed in the insulating layer 44 to expose a predetermined region of the redistribution line 46. A bump 52 is formed in the opening in the insulating layer 44, for example, via an under bump metallurgy (UBM) layer 50. The electronic device 100 is connected to a wiring substrate or the like via the bump 52, for example.

[0121] In this embodiment, one or more of the insulating layer 42 and the insulating layer 44 can be formed of a cured film formed by, for example, curing the above-mentioned photosensitive resin composition. In this case, for example, a coating film formed from the photosensitive resin composition is exposed to ultraviolet light, developed to form a pattern, and then heated and cured to form the insulating layer 42 or the insulating layer 44.

[0122] (Method for Manufacturing an Electronic Device) The method for manufacturing an electronic device of this embodiment includes a coating film formation step in which the photosensitive resin composition of this embodiment is applied to a substrate to form a coating film. The method for manufacturing an electronic device of this embodiment may further include an exposure step in which the formed coating film is exposed to light, a development step in which the exposed coating film is developed, and a heating step in which the coating film remaining after development is heated to harden the coating film and form a cured film. This results in a cured film of the photosensitive resin composition, which is used as the insulating layer 42 or 44 constituting the electronic device 100. The method for manufacturing an electronic device of this embodiment may further include a step of cleaning the coating film on the backside of the substrate after the coating film formation step. This allows for the removal of unnecessary coating film that has spread to the backside of the substrate when forming the coating film by spin coating or the like, thereby improving the edge shape of the cured film formed from the coating film. The photosensitive resin composition of this embodiment has an appropriate range of affinity with a back-rinse solvent used to remove unnecessary coating film during coating film formation, thereby ensuring an appropriate edge shape of the cured film. Specifically, the photosensitive resin composition of this embodiment has a moderately low affinity with a back-rinse solvent, which prevents the back-rinse solvent from seeping into the substrate surface, i.e., the coating film side of the photosensitive resin composition on the substrate, preventing the coating film from being inadvertently dissolved. When the coating film is pre-baked to form a cured film, the occurrence of unexpected steps or defects at the edges can be suppressed, resulting in a more favorable edge shape. Furthermore, the photosensitive resin composition of this embodiment has a moderately high affinity with a back-rinse solvent, which allows the back-rinse solvent to fulfill its original purpose of removing unnecessary photosensitive resin composition that has seeped into the back side of the substrate during coating film formation.

[0123] When the affinity of the photosensitive resin composition of this embodiment with the back-rinse solvent is evaluated by the following method, the penetration diameter of the back-rinse solvent is preferably 15 mm or more, more preferably 18 mm or more, even more preferably 20 mm or more, and preferably 28 mm or less, more preferably 26 mm or less, and even more preferably 23 mm or less. When the penetration diameter is below the upper limit (the back-rinse solvent does not penetrate too much), the affinity between the photosensitive resin composition and the back-rinse solvent can be appropriately reduced, resulting in a more favorable edge shape of the coating film. When the penetration diameter is above the lower limit (the back-rinse solvent penetrates moderately), the affinity between the photosensitive resin composition and the back-rinse solvent can be appropriately improved, allowing the unwanted coating film on the back surface of the substrate to be cleaned and removed as intended. The affinity between the photosensitive resin composition and the back-rinse solvent is evaluated by the following method. The photosensitive resin composition is spin-coated onto a substrate to a film thickness of 20 μm to form a coating film. Immediately after the coating film is formed, 7 mg of back-rinse solvent is dropped onto the coating film from a height of 5 cm from the surface of the coating film using a dropper. The penetration diameter (mm) of the back-rinse solvent on the coating film immediately after the dropping (the diameter of the part penetrated by the back-rinse solvent) is measured. As the back-rinse solvent, OK73 thinner (PGME / PGMEA = 7 / 3) manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.

[0124] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted.

[0125] EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0126] <Synthesis of Alkali-Soluble Resin 1> Alkali-soluble resin 1, which is a polyamide resin, was synthesized by the following procedure. In a four-necked glass separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube, 170.20 g (0.346 mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 206.58 g (0.800 mol) of diphenyl ether-4,4'-dicarboxylic acid represented by the following formula (DC2) with 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole monohydrate, 4.01 g (0.047 mol) of 5-aminotetrazole, 45.22 g (0.196 mol) of 4,4'-methylenebis(2-aminophenol) represented by the following formula (DA2), and 56.24 g (0.196 mol) of 4,4'-methylenebis(2-amino-3,6 dimethylphenol) represented by the following formula (DA3) were placed. Thereafter, 578.3 g of N-methyl-2-pyrrolidone was added to the separable flask, and the raw material components were dissolved. Next, a reaction was carried out for 5 hours at 90°C using an oil bath. Next, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the separable flask, and the reaction was carried out with stirring at 90°C for 2 hours, after which the reaction was terminated by cooling to 23°C.

[0127] The reaction mixture in the separable flask was filtered, and the resulting filtrate was poured into a solution of water / isopropanol = 7 / 4 (volume ratio). Thereafter, the precipitate was filtered off, thoroughly washed with water, and then dispersed in NMP (N-methylpyrrolidone) without drying, to obtain a solution of the target alkali-soluble resin 1. The weight-average molecular weight Mw of the obtained alkali-soluble resin 1 was 18,081.

[0128]

[0129]

[0130]

[0131] <Synthesis of Photosensitizer 1> Photosensitizer 1, which is a diazoquinone compound, was synthesized by the following procedure: In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.04 g (0.026 mol) of the compound represented by the following formula (P-1), 18.81 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 170 g of acetone were placed and stirred to dissolve.

[0132] Next, while cooling the flask in a water bath so that the temperature of the reaction solution did not exceed 35°C, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added and the reaction was continued for an additional 30 minutes. Next, the reaction mixture was filtered, and the filtrate was poured into a mixed solution of water / acetic acid (990 mL / 10 mL). Next, the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. As a result, photosensitizer 1 represented by the structure of the following formula (Q-1) was obtained.

[0133]

[0134] <Thermal crosslinking agent> Thermal crosslinking agent 1: paraxylene glycol (PXG, manufactured by Ihara Nikkei Chemical Industry Co., Ltd.) <Solubility enhancer> Solubility enhancer 1: 2,2'-methylene bisphenol (o,o'-BPF, manufactured by Honshu Chemical Industry Co., Ltd.) Solubility enhancer 2: compound of the following formula (2), manufactured by Air Water Inc.

[0135]

[0136] <Adhesion aids> Adhesion aid 1: 3-methacryloxypropyltrimethoxysilane Adhesion aid 2: 3-glycidoxypropyltriethoxysilane <Solvents> Solvent 1: γ-butyrolactone (GBL) Solvent 2: N-methyl-2-pyrrolidone (NMP) <Surfactants> Fluorine-based surfactant 1: FC4432, manufactured by 3M Japan Ltd., weight average molecular weight (Mw): 8202, maximum peak molecular weight: 16182, surface tension: 24.2 mN / m

[0137] <Synthesis of Polyether-Modified Polydimethylsiloxane 1> Polyether-modified polydimethylsiloxane 1 was synthesized with reference to Synthesis Example 2 in paragraph 0115 of JP 2002-079109 A, using a polyether compound of the following formula (3) instead of polydimethylsiloxane represented by the following formula (4) and dimethallyl polyether.

[0138]

[0139]

[0140] The obtained polyether-modified polydimethylsiloxane 1 had the above general formula (1) in which m was 3, p was 7, q was 0, x was 4, y was 3, and R was hydrogen. Note that m, p, q, x, and y in general formula (1) were determined from the structures of the polydimethylsiloxane represented by formula (4) above and the polyether compound represented by formula (3) above, which were used in the synthesis of polyether-modified polydimethylsiloxane 1.

[0141] The polystyrene-equivalent weight-average molecular weight of the obtained polyether-modified polydimethylsiloxane 1 was measured by gel permeation chromatography (described later) and found to be 1730. The polystyrene-equivalent weight-average molecular weight of the maximum peak of the molecular weight distribution was 2234, and the Mw / Mn was 2.23. The surface tension of the polyether-modified polydimethylsiloxane 1 was 29.4 mN / m, the density was 1.037±0.030 g / mL, the refractive index was 1.433±0.010, and the nonvolatile content was 96.25±3.75%.

[0142] <Synthesis of Polyether-Modified Polydimethylsiloxane 2> Polyether-modified polydimethylsiloxane 2 was synthesized in a similar manner to the synthesis of polyether-modified polydimethylsiloxane 1 described above, except that the types and compounding ratios of the polydimethylsiloxane and polyether compound were changed. The obtained polyether-modified polydimethylsiloxane 2 had the general formula (1) above, where m was 3, p was 3, q ​​was 5, x was 3, y was 3, and R was hydrogen. In general formula (1), m, p, q, x, and y were determined from the structures of the polydimethylsiloxane and polyether compound used in the synthesis of polyether-modified polydimethylsiloxane 2. Furthermore, the obtained polyether-modified polydimethylsiloxane 2 had a polystyrene-equivalent weight-average molecular weight of 5821, a polystyrene-equivalent weight-average molecular weight of the maximum peak of the molecular weight distribution of 7367, and an Mw / Mn of 2.77, as measured by gel permeation chromatography described below.

[0143] (Density, Refractive Index, and Nonvolatile Content) The density of the polyether-modified polydimethylsiloxane was measured at 20°C in accordance with ISO 2811-3:2011. The refractive index of the polyether-modified polydimethylsiloxane was measured in accordance with DIN 51423. The nonvolatile content of the polyether-modified polydimethylsiloxane was measured at 105°C for 1 hour in accordance with ISO 3251:2019.

[0144] (Molecular Weight Measurement of Alkali-Soluble Resin by Gel Permeation Chromatography) The weight average molecular weight (Mw) of the alkali-soluble resin was measured by the following method. Apparatus: Gel permeation chromatography apparatus manufactured by JASCO Corporation Pump: PU980 manufactured by JASCO Corporation Column oven: CO-965 manufactured by JASCO Corporation Sampler: AS-2055 manufactured by JASCO Corporation Column: Gelpack GL-83COMDT-5P manufactured by Hitachi High-Technologies Corporation Detector: RI detector for liquid chromatography Measurement temperature: 40°C Solvent: THF Flow rate: 0.350 mL / min Sample concentration in measurement solution: 2.0 mg / mL

[0145] (Molecular weight measurement of polyether-modified polydimethylsiloxane by gel permeation chromatography) For the polyether-modified polydimethylsiloxane and the fluorosurfactant, the weight average molecular weight (Mw), number average molecular weight (Mn), and weight average molecular weight of the maximum peak in the polystyrene-equivalent molecular weight distribution were measured by the following methods: Gel permeation chromatography apparatus HLC-8320GPC manufactured by Tosoh Corporation Peak separation software: Eco-SEC manufactured by Tosoh Corporation Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatogram Measurement temperature: 40°C Solvent: THF Flow rate: 0.35 mL / min Sample concentration in measurement solution: 2.0 mg / mL

[0146] (Surface Tension) The surface tension (mN / m) of the polyether-modified polydimethylsiloxane and the fluorine-based surfactant was measured at 23° C. in a 1% GBL solution using a contact angle meter (DMs-401, Kyowa Interface Science Co., Ltd.).

[0147] (Preparation of Photosensitive Resin Compositions and Evaluation of Antifoaming Properties) Photosensitive resin compositions of Examples and Comparative Examples were prepared as follows, and antifoaming properties were evaluated. Each raw material component other than the polyether-modified polydimethylsiloxane and the fluorine-based surfactant was added to a stirring vessel (bottom area: 70 cm) according to the formulation in Table 1 so that the total amount of the photosensitive resin composition was 500 mL. ２ ) and stirred under conditions of a temperature of 23°C, a stirring blade height of 1.0 cm from the bottom, a rotation speed of 250 rpm, a stirring time of 3 hours, and a nitrogen atmosphere. After stirring was completed, a surfactant was added according to the formulation in Table 1, and the mixture was stirred under conditions of a temperature of 23°C, a stirring blade height of 1.0 cm from the bottom, a rotation speed of 100 rpm, a stirring time of 30 minutes, and a nitrogen atmosphere to obtain a photosensitive resin composition of each example. Immediately after production, 5 mL of the obtained photosensitive resin composition was placed in a 20 mL graduated cylinder and allowed to stand for 15 hours at 23°C. The foam height (mm) after 15 hours was measured. The results are shown in Table 1. Note that a lower foam height indicates better defoaming properties.

[0148]

[0149] <Evaluation of Affinity for Back-Rinse Solvents> The affinity of the photosensitive resin compositions of Example 1 and Comparative Examples 1 to 3 obtained above for back-rinse solvents was evaluated using the following procedure. Comparative Example 4, which did not contain polyether-modified polydimethylsiloxane or fluorosurfactant, was also evaluated. The composition of Comparative Example 4 was the same as that of Example 1, except that polyether-modified polydimethylsiloxane 1 was omitted. Each photosensitive resin composition was spin-coated onto a substrate to form a coating film with a thickness of 10 μm. Immediately after the coating film was formed, approximately 7 mg of back-rinse solvent (OK73 Thinner, PGME / PGMEA = 7 / 3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the coating film from a height of 5 cm from the coating film surface using a dropper. The penetration diameter (mm) of the back-rinse solvent on the coating film immediately after the drop was measured (the diameter of the portion penetrated by the back-rinse solvent). The results are shown in Table 2.

[0150]

[0151] This application claims priority based on Japanese Patent Application No. 2023-055060, filed March 30, 2023, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. An alkali-soluble resin (A), a polyether-modified polydimethylsiloxane (B), a solvent (C), and a photosensitizer (D), The photosensitive resin composition, wherein the polyether-modified polydimethylsiloxane (B) has a weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography, of 1,000 or more and 5,000 or less.

2. the solvent (C) contains a solvent (C1), 2. The photosensitive resin composition according to claim 1, wherein the solvent (C1) comprises at least one selected from the group consisting of γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, propylene glycol monomethyl ether, 3-methyl-2-oxazolidinone, 3-methoxy-N,N-dimethylpropanamide, and propylene glycol monomethyl ether acetate.

3. The photosensitive resin composition according to claim 2, wherein the content of the solvent (C1) in the solvent (C) is 50% by mass or more and 100% by mass or less with respect to the total amount of the solvent (C).

4. 4. The photosensitive resin composition according to claim 1, wherein the polyether-modified polydimethylsiloxane (B) comprises a polyether-modified polydimethylsiloxane having a ratio (Mw / Mn) of the weight average molecular weight (Mw) in terms of polystyrene to the number average molecular weight (Mn) of 1 or more and 10 or less, as measured by gel permeation chromatography.

5. 4. The photosensitive resin composition according to claim 1, wherein the polyether-modified polydimethylsiloxane (B) comprises a polyether-modified polydimethylsiloxane having a weight-average molecular weight of 1,000 or more and 5,000 or less at a maximum peak in a molecular weight distribution in terms of polystyrene, as measured by gel permeation chromatography.

6. 4. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) has a weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography, of 5,000 or more and 70,000 or less.

7. 4. The photosensitive resin composition according to claim 1, wherein the content of the polyether-modified polydimethylsiloxane (B) is 10 ppm or more and 3000 ppm or less based on the entire photosensitive resin composition.

8. The photosensitive resin composition according to any one of claims 1 to 3, further comprising an adhesion aid (E).

9. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyether-modified polydimethylsiloxane (B) comprises a polyether-modified polydimethylsiloxane represented by the following general formula (1): 【Chemical 1】 (In the general formula (1), m is an average value of 1 or more and 5 or less, p is an average value of 1 or more and 10 or less, and q is an average value of 0 or more and less than 1. R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)

10. 10. The photosensitive resin composition according to claim 9, wherein, in the general formula (1), x has an average value of 1 or more and 50 or less, and y has an average value of 1 or more and 10 or less.

11. 10. The photosensitive resin composition according to claim 9, wherein x / y in the general formula (1) is 1 or more and 5 or less.

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

13. An electronic device comprising the cured film of claim 12.

14. A method for producing an electronic device, comprising a step of forming a coating film on a substrate using the photosensitive resin composition according to any one of claims 1 to 3.

15. further comprising the step of cleaning the coating on the backside of the substrate. The method for manufacturing an electronic device according to claim 14.

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