Method for manufacturing semiconductor device, and composition for forming upper layer film

Abstract

The present invention addresses the problem of providing: a method for manufacturing a semiconductor device, the method making it possible to manufacture a rewiring layer provided with a pattern having excellent dimensional uniformity; and a composition for forming an upper layer film. A method for manufacturing a semiconductor device according to the present invention includes: a preparation step for preparing a semiconductor element; and a rewiring layer formation step for forming a rewiring layer that is connected to the semiconductor element and is provided with an insulating part and a conductive part. The rewiring layer formation step includes, for example, a step for forming, on a photosensitive resin composition layer with a dissolution rate in an organic solvent decreasing upon exposure, an upper layer film with a transmittance at an exposure wavelength increasing upon exposure.

Description

Method for manufacturing semiconductor devices, and composition for forming upper layers

[0001] The present invention relates to a method for manufacturing semiconductor devices and a composition for forming an upper layer film.

[0002] The semiconductor device manufacturing process is divided into a front-end process, in which elements such as transistors and integrated circuits are formed on the surface of a silicon wafer, and a back-end process, in which semiconductor chips obtained by separating the silicon wafer on which integrated circuits and other elements are formed are packaged. In the back-end process, multiple semiconductor chips and a package substrate are sometimes electrically connected via an interposer having conductive parts such as wiring. In addition to Si interposers, a redistribution layer (RDL) made of resin, which has insulating and conductive parts, is used as an organic interposer from the viewpoint of low cost, etc.

[0003] Incidentally, in the front-end processes of semiconductor device manufacturing, a method for forming a resist pattern using a contrast enhancement layer (CEL) is known as a technique for improving the resolution of a photosensitive resin composition (see, for example, Patent Documents 1 and 2).

[0004] Japanese Patent Publication No. 05-241349 Japanese Patent Publication No. 2010-230995

[0005] In recent years, there has been a demand for miniaturization not only of the wiring manufactured in the front-end process of semiconductor devices, but also of the wiring in the redistribution layer manufactured in the back-end process of semiconductor devices. The present inventors found that when they applied photodecolorizable materials (organic materials whose transmittance to the exposure wavelength increases with exposure; the same applies hereinafter) described in Patent Documents 1 and 2, etc., to form the redistribution layer, the dimensional uniformity of the pattern was poor.

[0006] Therefore, the object of the present invention is to provide a method for manufacturing a semiconductor device and a composition for forming an upper film that can produce a redistribution layer having a pattern with excellent dimensional uniformity.

[0007] As a result of diligent study on the above problems, the inventors of the present invention have found that by having a redistribution layer formation process with predetermined processing steps, it is possible to manufacture a redistribution layer with a pattern that has excellent dimensional uniformity, and have completed the present invention. That is, the inventors of the present invention have found that the above problems can be solved by the following configuration.

[0008] [1] A method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises, in this order: a step 1 for applying a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer whose dissolution rate into an organic solvent decreases upon exposure; a step 2 for forming an upper layer film on the photosensitive resin composition layer whose transmittance with respect to the exposure wavelength increases upon exposure; a step 3 for pattern exposure of the laminate of the photosensitive resin composition layer and the upper layer film; a step 4 for removing the unexposed portion of the photosensitive resin composition layer and the upper layer film in the laminate with a developer containing the organic solvent to obtain a negative-type pattern consisting of the exposed portion of the photosensitive resin composition layer; and a step 5 for forming a conductive portion using the negative-type pattern as a template by plating. [2] The method for manufacturing a semiconductor device according to [1], wherein the upper layer film has a transmittance of 10% or more with respect to the exposure wavelength upon exposure. [3] A method for manufacturing a semiconductor device according to [1] or [2], wherein the exposure wavelength for the pattern exposure is 350 to 410 nm. [4] A method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the exposure wavelength for the pattern exposure is 365 nm. [5] A method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the SP value of the developer is greater than the SP value of the solvent used to form the upper layer film. [6] A method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the developer contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene. [7] A method for manufacturing a semiconductor device according to any one of [1] to [6], wherein the insulating portion contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. [8] A method for manufacturing a semiconductor device according to any one of [1] to [7], wherein the photosensitive resin composition is a crosslinked negative composition.[9] A method for manufacturing a semiconductor device according to any one of [1] to [7], wherein the photosensitive resin composition is a chemically amplified polarity conversion negative type composition.

[10] A method for manufacturing a semiconductor device according to any one of [1] to [9], wherein the pattern exposure is exposure by a laser direct imaging method.

[11] A composition for forming an upper layer film used in a method for manufacturing a semiconductor device according to any one of [1] to

[10] , comprising a photodecolorizable material.

[0009] According to the present invention, a method for manufacturing a semiconductor device and a composition for forming an upper film can be provided, which can produce a redistribution layer having a pattern with excellent dimensional uniformity.

[0010] Figure 1A is a schematic cross-sectional view illustrating step 1 in the redistribution layer formation process, showing a schematic diagram of a cross-section along the thickness direction of the substrate 1 and the photosensitive resin composition layer 2. Figure 1B is a schematic cross-sectional view illustrating step 2 in the redistribution layer formation process, showing a schematic diagram of a cross-section along the thickness direction of the substrate 1, the photosensitive resin composition layer 2, and the upper film 3. Figure 1C is a schematic cross-sectional view illustrating step 3 in the redistribution layer formation process, showing how a portion 3a with increased transmittance in the upper film 3 and an exposed portion 2a in the photosensitive resin composition layer are created by pattern exposure from the position of the arrow. Figure 1D is a schematic cross-sectional view illustrating step 4 in the redistribution layer formation process, showing how the unexposed portion 2b of the photosensitive resin composition layer and the upper film 3 are removed, and a negative-type pattern consisting of the exposed portion 2a of the photosensitive resin composition layer is formed. Figure 1E is a schematic cross-sectional view illustrating step 5 in the redistribution layer formation process, showing how the conductive portion 4 is formed using the negative-type pattern as a template.

[0011] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.

[0012] [Method for Manufacturing Semiconductor Devices] The present invention provides a method for manufacturing semiconductor devices, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and comprising an insulating portion and a conductive portion. Furthermore, the present invention provides a method for manufacturing semiconductor devices in which the redistribution layer formation step comprises the following steps 1 to 5 in this order: Step 1: A step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer whose dissolution rate into an organic solvent decreases upon exposure. Step 2: A step of forming an upper layer film on the photosensitive resin composition layer, whose transmittance to the exposure wavelength increases upon exposure. Step 3: A step of pattern exposure of the laminate of the photosensitive resin composition layer and the upper layer film. Step 4: A step of removing the unexposed portion of the photosensitive resin composition layer and the upper layer film in the laminate using a developer containing the organic solvent to obtain a negative pattern consisting of the exposed portion of the photosensitive resin composition layer. Step 5: A step of forming a conductive portion using the negative pattern as a template by plating.

[0013] As described above, the semiconductor device manufacturing method of the present invention makes it possible to manufacture a redistribution layer with a pattern that has excellent dimensional uniformity. The reasons for this are generally estimated to be as follows. First, in the formation of a redistribution layer, especially in the manufacture of a large package (for example, about 50 mm x 50 mm), a difference in development time tends to occur between the center and the periphery. Therefore, in a miniaturized redistribution layer, even a slight difference in development time can cause overdevelopment or underdevelopment, and the desired resolution may not be obtained. Also, as shown in Comparative Example 3 described later, when forming a negative-type pattern with an alkaline developer, the selection of solvents for forming the upper layer film is limited, making it difficult to manufacture a redistribution layer with a pattern that has excellent dimensional uniformity. Therefore, in the present invention, by forming a negative-type pattern with a developer containing an organic solvent, the above-mentioned problems can be resolved even when an upper layer film is formed. The following describes in detail each step of the semiconductor device manufacturing method of the present invention.

[0014] [Preparation Process] The preparation process is the process of preparing the semiconductor device. Here, the semiconductor device may have a metal wiring layer and terminals electrically connected to the metal wiring layer in order to electrically connect to the redistribution layer described later.

[0015] The function of a semiconductor device is distinguished by its operation. Examples of semiconductor functions include computation (CPU, GPU, etc.), storage (memory, etc.), conversion (converter, etc.), filtering, and sensing. When these functions are integrated into a single chip or unit, the function is identified in that integrated state. If the identified functions differ, they are considered different semiconductor devices.Specific examples of semiconductor devices include logic LSI (Large Scale Integration), ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), ASSP (Application Specific Standard Product), microprocessors (e.g., CPU, GPU, etc.), memory (e.g., DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), HMC (Hybrid Memory Cube), MRAM (Magnetic RAM), PCM (Phase-Change Memory), ReRAM (Resistive RAM), FeRAM (Ferroelectric RAM), flash memory, etc.), LED (Light Emitting Diode), power semiconductor devices, analog IC (Integrated Circuit), DC (Direct Current)-DC (Direct Current) converters, insulated gate bipolar transistors (IGBTs), accelerometers, pressure sensors, oscillators, gyroscopes, and other MEMS (Micro Electro Mechanical Systems), GPS (Global Positioning System), and FM (Frequency Examples include Modulation, NFC (Nearfield Communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network), discrete components, BSI (Back Side Illumination), CIS (Contact Image Sensor), camera modules, passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, RFIPD (Radio Frequency Integrated Passive Devices), and BB (Broadband).

[0016] [Redistribution Layer Formation Process] The redistribution layer formation process is a process for forming a redistribution layer that is connected to the semiconductor element and has an insulating portion and a conductive portion, and is a process that has steps 1 to 5 described later in this order. Here, the redistribution layer formed in the redistribution layer formation process has an insulating portion and a conductive portion as described above, but is usually a multilayer wiring structure in which multiple redistributions (conductive portions) are separated by multiple interlayer insulating films (insulating portions), and refers to a layer consisting of one set of redistributions and an interlayer insulating film formed thereon. Note that there are also cases in which the redistribution layer consists of only one layer.

[0017] <Step 1: Formation of a Photosensitive Resin Composition Layer> Step 1 is a step in which a photosensitive resin composition is applied to a substrate to form a photosensitive resin composition layer in which the rate of dissolution in an organic solvent decreases upon exposure. Here, "the rate of dissolution in an organic solvent decreases upon exposure" refers to the characteristic in which the exposed area is altered by pattern exposure in Step 3, described later, and its solubility in the developer decreases compared to the unexposed area which is removed by the developer containing an organic solvent used in Step 4, described later. By forming a photosensitive resin composition layer in Step 1 in which "the rate of dissolution in an organic solvent decreases upon exposure," a negative-type pattern (a pattern in which the unexposed area is removed and the exposed area remains; the same applies hereinafter) can be obtained in Step 4, described later. In other words, "the rate of dissolution in an organic solvent decreases upon exposure" can be said to be synonymous with "using a negative-type photosensitive resin composition." Details of the photosensitive resin composition will be explained later.

[0018] Figure 1A is a schematic cross-sectional view illustrating step 1, showing a cross-section along the thickness direction of the substrate 1 and the photosensitive resin composition layer 2. In step 1, the photosensitive resin composition is applied to the substrate 1 to form the photosensitive resin composition layer 2. In the example of Figure 1A, an example is shown in which the photosensitive resin composition layer 2 is formed in contact with the substrate 1, but the process is not limited to this, and the photosensitive resin composition layer 2 may be formed on the substrate 1 via other layers not shown. In the example of Figure 1A, an example is shown in which the photosensitive resin composition layer 2 is formed over the entire surface of one side of the substrate 1, but the process is not limited to this, and the photosensitive resin composition layer 2 may be formed on at least a part of one side of the substrate 1. Furthermore, the photosensitive resin composition layer 2 may be formed on both sides of the substrate 1.

[0019] Coating is a preferred method for applying the photosensitive resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of both uniformity of film thickness and productivity, spin coating or slit coating are more preferred. By adjusting the solid content concentration of the photosensitive resin composition and the application conditions according to the application method, a film of the desired thickness can be obtained. Alternatively, a method can be applied in which a coating film formed on a temporary support using the above application method is transferred onto the substrate.

[0020] Step 1 may include a heat treatment (soft bake) in which the photosensitive resin composition applied to the substrate is heated. This removes components such as solvents from the photosensitive resin composition applied to the substrate. The heating temperature in the heat treatment is preferably 50 to 150°C. Heating may also be performed under reduced pressure. The heating time is preferably 30 seconds to 20 minutes.

[0021] In the present invention, it is preferable that the photosensitive resin composition contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, due to its excellent insulating properties, chemical stability, and mechanical properties. Details of these resin materials will be described later. For similar reasons, it is preferable that the insulating portion of the redistribution layer is formed by the photosensitive resin composition, and that the insulating portion contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

[0022] Furthermore, in the present invention, from the viewpoint of improving pattern strength through crosslinking and easily maintaining the shape as a mold for plating, it is preferable to use a crosslinked negative type composition as the photosensitive resin composition, that is, a composition in which the molecular weight etc. increases due to the crosslinking reaction and the solubility of the exposed area in the developer decreases. Details of the crosslinked negative type composition will be described later.

[0023] Furthermore, in the present invention, it is preferable to use a chemically amplified polarity-converting negative type composition as the photosensitive resin composition, as this provides excellent resolution and sensitivity. Hereinafter, an embodiment of the chemically amplified polarity-converting negative type composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor will be described.

[0024] On the other hand, another preferred embodiment of the chemically amplified polarity-converting negative composition is one which contains a resin whose polarity changes due to the action of an acid (hereinafter also abbreviated as "resin (B)") and a photoacid generator.

[0025] (Resin (B)) Resin (B) is preferably a resin whose polarity increases due to the action of an acid and whose solubility in organic solvent developer decreases, and more preferably a resin having a group that decomposes due to the action of an acid to produce polar groups (hereinafter also called "acid-degradable group") (hereinafter also called "acid-degradable resin"). Polarity refers to an uneven distribution of positive and negative charges. When resin (B) is an acid-degradable resin, the glass transition temperature (Tg) of the exposed area (where polar groups are generated) tends to be higher than that of the unexposed area, so the penetration of the plating solution is suppressed and the resistance to stress during plating formation is increased, thereby improving the plating resistance.

[0026] An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group that decomposes and is eliminated upon the action of an acid. The polar groups are not particularly limited as long as they are groups that become poorly soluble or insoluble in a developer solution containing an organic solvent, but examples include acidic groups such as phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, which is conventionally used as a developer solution for resists), or alcoholic hydroxyl groups.

[0027] Alcoholic hydroxyl groups refer to hydroxyl groups bonded to a hydrocarbon group, excluding hydroxyl groups directly bonded to an aromatic ring (phenolic hydroxyl groups), and exclude aliphatic alcohols in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom (for example, fluorinated alcohol groups (hexafluoroisopropanol groups, etc.)). Preferably, the alcoholic hydroxyl group has a pKa (acid dissociation constant) of 12 to 20.

[0028] As the polar group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.

[0029] As the acid-decomposable group, a group obtained by substituting a hydrogen atom of these groups with an acid-eliminable group is preferable. Examples of the acid-eliminable group (leaving group) include -C(R ３６ )(R ３７ )(R ３８ ), -C(R ３６ )(R ３７ )(OR ３９ ), and -C(R ０１ )(R ０２ )(OR ３９ ), and the like. In the formula, R ３６ to R ３９ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ３６ and R ３７ may be bonded to each other to form a ring. R ０１ and R ０２ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0030] As for R ３６ to R ３９ , R ０１ and R ０２ , an alkyl group having 1 to 8 carbon atoms is preferable as the alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. R ３６ to R ３９ , R ０１ and R ０２The cycloalkyl group may be monocyclic or polycyclic. As a monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferred, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As a polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, such as an adamantyl group, a norbornyl group, an isobolonyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, and an androstanyl group. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. ３６ ~R ３９ , R ０１ and R ０２ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. ３６ ~R ３９ , R ０１ and R ０２ The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, and a naphthylmethyl group. ３６ ~R ３９ , R ０１ and R ０２ The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. ３６ and R ３７ The ring formed by the bonding of these groups is preferably a cycloalkyl group (monocyclic or polycyclic). Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferred, and monocyclic cycloalkyl groups having 5 carbon atoms are even more preferred.

[0031] The resin (B) preferably has repeating units represented by the following formula (B).

[0032] Formula (B)

[0033] In formula (B), R represents a group that is removed by an acid (leaving group), and X represents a hydrogen atom or a methyl group. Specific examples of the leaving group and preferred embodiments are as described above.

[0034] The resin (B) preferably has repeating units represented by the following formula (AI) as repeating units having acid-degradable groups. The repeating units represented by formula (AI) generate carboxyl groups as polar groups upon the action of an acid, and exhibit high interaction through hydrogen bonding among multiple carboxyl groups.

[0035]

[0036] In formula (AI), Xa １ Rx represents a hydrogen atom, alkyl group, cyano group, or halogen atom. T represents a single bond or divalent linking group. １ ~Rx ３ Each of these independently represents an alkyl group or a cycloalkyl group. Rx １ ~Rx ３ These two may combine to form a ring structure.

[0037] Examples of divalent linking groups for T include alkylene groups, -COO-Rt-, -O-Rt-, and phenylene groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or -COO-Rt-. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ -, - (CH ２ ) ２ - or - (CH ２ ) ３ - is more preferable. T is more preferably a single bond.

[0038] X ａ１ The alkyl group may have substituents, and examples of substituents include hydroxyl groups and halogen atoms (preferably fluorine atoms). ａ１The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, hydroxymethyl, and trifluoromethyl groups, with methyl being preferred. ａ１ A hydrogen atom or a methyl group is preferred.

[0039] Rx １ Rx ２ and Rx ３ The alkyl group may be linear or branched, and is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Rx １ Rx ２ and Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.

[0040] Rx １ Rx ２ and Rx ３ The ring structure formed by the bonding of these two is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring and a cyclohexyl ring, or a polycyclic cycloalkyl group such as a norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring, with a monocyclic cycloalkane ring having 5 or 6 carbon atoms being more preferred.

[0041] Rx １ Rx ２ and Rx ３ Each of these is preferably an alkyl group, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

[0042] Each of the above groups may have substituents, and examples of substituents include alkyl groups (1 to 4 carbon atoms), cycloalkyl groups (3 to 8 carbon atoms), halogen atoms, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms), with a carbon number of 8 or less being preferred. In particular, from the viewpoint of further improving the solubility contrast in developing solutions containing organic solvents before and after acid decomposition, substituents that do not have heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms are more preferred (for example, alkyl groups substituted with hydroxyl groups are more preferred), groups consisting only of hydrogen atoms and carbon atoms are even more preferred, and linear or branched alkyl groups or cycloalkyl groups are particularly preferred.

[0043] In equation (AI), Rx １ ~Rx ３ Each of these is an alkyl group, and Rx １ ~Rx ３ It is preferable that the two do not combine to form a ring structure. This ensures that the -C(Rx) group decomposes and is eliminated by the action of acid. １ ) (Rx ２ ) (Rx ３ This suppresses the increase in volume of the base represented by ), and tends to suppress volume contraction of the exposed area in the exposure process and the post-exposure heating process which may be performed after the exposure process.

[0044] The following are specific examples of repeating units represented by formula (AI), but the present invention is not limited to these specific examples. In the specific examples, Rx is a hydrogen atom, CH ３ CF ３ , or CH ２ This represents an OH group. Rxa and Rxb each independently represent an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms). Xa １ is a hydrogen atom, CH ３ CF ３ , or CH ２ This represents OH. Z represents a substituent, and if there are multiple Zs, they may be the same or different from each other. p represents 0 or a positive integer. Specific and preferred examples of Z are Rx １ ~Rx ３These are similar to the specific examples and preferred examples of substituents that each of the groups may have.

[0045]

[0046]

[0047]

[0048] Furthermore, it is preferable that the resin (B) has repeating units having acid-degradable groups, as described in paragraphs

[0057] to

[0071] of Japanese Patent Application Publication No. 2014-202969.

[0049] Furthermore, resin (B) may have repeating units having acid-degradable groups, which generate alcoholic hydroxyl groups as described in paragraphs

[0072] to

[0073] of Japanese Patent Application Publication No. 2014-202969.

[0050] The repeating unit having an acid-degradable group may be of one type or two or more types may be used in combination.

[0051] The content of repeating units having acid-degradable groups in resin (B) (the total if there are multiple repeating units having acid-degradable groups) is preferably 20 to 90 mol%, and more preferably 40 to 80 mol%, relative to the total repeating units of resin (B), for reasons that the effects of the present invention are superior. In particular, it is preferable that resin (B) has repeating units represented by the above formula (AI), and that the content of repeating units represented by the above formula (AI) relative to the total repeating units of resin (B) is 40 mol% or more.

[0052] Resin (B) may contain other repeating units. Examples of other repeating units include repeating units having at least one selected from the group consisting of lactone structures, sultone structures, and carbonate structures; repeating units having hydroxyl groups or cyano groups; repeating units having acidic groups; and repeating units having an alicyclic hydrocarbon structure without polar groups (e.g., acidic groups, hydroxyl groups, cyano groups, etc.) and not exhibiting acid degradability. Details of such other repeating units can be found in paragraphs

[0121] to

[0161] of International Publication No. 2016 / 208300, which are incorporated herein by reference.

[0053] The weight-average molecular weight (Mw) of resin (B) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000. By setting the weight-average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability and viscosity that leads to deterioration of film formation can be prevented. The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. The smaller the molecular weight distribution, the better the resolution and resist shape, the smoother the sidewalls of the resist pattern, and the better the roughness.

[0054] The content of resin (B) is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, relative to the total solid content of the chemically amplified polarity conversion negative type composition. There is no particular upper limit, but it is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. Resin (B) may be used alone or in combination of multiple types.

[0055] (Photoacid Generator) The photoacid generator is not particularly limited, but it is preferably a compound that generates an organic acid upon irradiation with active light or radiation. The photoacid generator may be contained in the resin (B) and / or a resin other than resin (B) described above. More specifically, the photoacid generator may be linked to resin (B) and / or a resin other than resin (B) via a chemical bond. As the photoacid generator, known compounds and mixtures thereof that generate acid upon irradiation with active light or radiation, used as photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorizers and photocolor changers for dyes, and microresists, can be appropriately selected and used. For example, the compounds described in paragraphs

[0039] to

[0103] of Japanese Patent Application Publication No. 2010-061043 and the compounds described in paragraphs

[0284] to

[0389] of Japanese Patent Application Publication No. 2013-004820 can be cited, but the present invention is not limited thereto. Examples of photoacid generators include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oximesulfonates, diazodisulfones, disulfones, and o-nitrobenzylsulfonates.

[0056] The photoacid generator is preferably a photoacid generator that generates an acid without a fluoride alkyl group. When such a photoacid generator is used, the impact on the plating process can be suppressed, resulting in better performance such as resistance to collapse. The photoacid generator is preferably a nonionic type photoacid generator.

[0057] The photoacid generator is preferably a compound having at least one group selected from the group consisting of an oximesulfonate group and an imidosulfonate group, a compound having at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation, a diazosulfone compound, and a disulfone compound. It is believed that using these compounds improves the efficiency of acid generation by exposure, and facilitates the efficient bonding between the acid group and the vinyl ether group compound.

[0058] Compounds having an oximesulfonate group (hereinafter also referred to as "oximesulfonate compounds") are not particularly limited as long as they have an oximesulfonate group, but it is preferable that they be oximesulfonate compounds represented by formulas (OS-103), (OS-104), and (OS-105).

[0059]

[0060] In formulas (OS-103) to (OS-105), R １１ R represents an alkyl group, aryl group, or heteroaryl group, and there are multiple R groups. １２ Each of these independently represents a hydrogen atom, alkyl group, aryl group, or halogen atom, and there are multiple R groups. １６ Each of these independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, where X represents O or S, n represents 1 or 2, and m represents an integer from 0 to 6.

[0061] In the above formulas (OS-103) to (OS-105), R １１ The alkyl group, aryl group, or heteroaryl group represented by may have substituents. In the above formulas (OS-103) to (OS-105), R １１ The alkyl group represented by is preferably an alkyl group having a total of 1 to 30 carbon atoms, which may have substituents. １１ The substituents that the alkyl group represented by may have include halogen atoms, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, and aminocarbonyl groups.

[0062] In the above formulas (OS-103) to (OS-105), R １１ Examples of alkyl groups that can be represented include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group.

[0063] Furthermore, in the above formulas (OS-103) to (OS-105), R １１ The aryl group represented by is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent. R １１ Examples of the substituent which the aryl group represented by may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

[0064] R １１ Preferable examples of the aryl group represented by include a phenyl group, a p-methylphenyl group, a trimethylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.

[0065] Furthermore, in the above formulas (OS-103) to (OS-105), R １１ The heteroaryl group represented by is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent. R １１ Examples of the substituent which the heteroaryl group represented by may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

[0066] In the above formulas (OS-103) to (OS-105), R １１ The heteroaryl group represented by only needs to have at least one heteroaromatic ring, and for example, a heteroaromatic ring and a benzene ring may be condensed. R １１ Examples of the heteroaryl group represented by include a group obtained by removing one hydrogen atom from a ring selected from the group consisting of an optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring, and benzimidazole ring.

[0067] In the above formulas (OS-103) to (OS-105), R １２ is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. In the above formulas (OS-103) to (OS-105), among two or more R １２ groups present in the compound, it is preferable that one or two of them are an alkyl group, an aryl group or a halogen atom, more preferable that one of them is an alkyl group, an aryl group or a halogen atom, and particularly preferable that one of them is an alkyl group and the remainder are hydrogen atoms. In the above formulas (OS-103) to (OS-105), the alkyl group or aryl group represented by R １２ may have a substituent. Examples of the substituent that the alkyl group or aryl group represented by R １２ may have include the same groups as the substituents that the alkyl group or aryl group for R １ may have.

[0068] In the above formulas (OS-103) to (OS-105), as the alkyl group represented by R １２ , an alkyl group having a total of 1 to 12 carbon atoms which may have a substituent is preferable, and an alkyl group having a total of 1 to 6 carbon atoms which may have a substituent is more preferable. As the alkyl group represented by R １２ , a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, an n-hexyl group, an allyl group, a chloromethyl group, a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group are more preferable; a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are still more preferable; and a methyl group is particularly preferable.

[0069] In the above formulas (OS-103) to (OS-105), as the aryl group represented by R １２ , an aryl group having a total of 6 to 30 carbon atoms which may have a substituent is preferable. R １２The preferred aryl group represented by is a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group. １２ Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms. Among these, chlorine and bromine atoms are preferred.

[0070] In the above formulas (OS-103) to (OS-105), X represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring. In the above formulas (OS-103) to (OS-105), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is preferably 2.

[0071] In the above formulas (OS-103) to (OS-105), R １６ The alkyl group and alkyloxy group represented by the above formula (OS-103) to (OS-105) may have substituents. １６ The alkyl group represented by is preferably an alkyl group having a total of 1 to 30 carbon atoms, which may have substituents. １６ The substituents that the alkyl group represented by may have include halogen atoms, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, and aminocarbonyl groups.

[0072] In the above formulas (OS-103) to (OS-105), R １６ Preferred alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, and benzyl groups.

[0073] In the above formulas (OS-103) to (OS-105), R １６The alkyloxy group represented is preferably an alkyloxy group having a total of 1 to 30 carbon atoms, which may have substituents. １６ The substituents that the alkyloxy group represented by may have include halogen atoms, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, and aminocarbonyl groups.

[0074] In the above formulas (OS-103) to (OS-105), R １６ The alkyloxy group represented by is preferably a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group. １６ Examples of aminosulfonyl groups in this context include methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, and aminosulfonyl group. １６ Examples of alkoxysulfonyl groups represented by include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, and butyloxysulfonyl group.

[0075] Furthermore, in the above formulas (OS-103) to (OS-105), m represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0076] Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture of both.

[0077] Specific examples of compounds represented by formula (OS-101) that can be suitably used in the present invention include, but are not limited to, the compounds described in paragraphs 0092 to 0097 of International Publication No. 2015 / 064602. Commercial products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (structure shown below, manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (structure shown below, manufactured by Midori Chemical Co., Ltd.), and the like.

[0078] Examples of compounds having an imidosulfonate group (hereinafter also referred to as "imidosulfonate compounds") include the compound represented by the general formula (ZV).

[0079]

[0080] In the general formula (ZV), R ２０８ represents an alkyl group or aryl group. A represents an alkylene group, an alkenylene group, or an arylene group. If the alkyl group is a cyclic alkyl group, it may form a ring via a carbonyl group. R ２０８ The alkyl group is preferably a linear alkyl group or a cyclic alkyl group. ２０８ The group is preferably a linear or branched alkyl group or an aryl group. These groups may or may not be substituted. Furthermore, if the alkyl group is a cyclic alkyl group, it may form a ring via a carbonyl group, and the cyclic alkyl group may be polycyclic. Preferably, the group is a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, or norbonyl group). ２０８ The alkyl group may be further substituted with, for example, a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group.

[0081] R ２０８ The aryl group is preferably a phenyl group or a naphthyl group. ２０８の The aryl group may be further substituted with, for example, a halogen atom, an alkoxy group (e.g., C1-C5), a hydroxyl group, a cyano group and / or a nitro group, but preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, or a norbonyl group).

[0082] Examples of alkylene groups in A include alkylene groups having 1 to 12 carbon atoms (e.g., methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), examples of alkenylene groups in A include alkenylene groups having 2 to 12 carbon atoms (e.g., etenylene group, propenylene group, butenylene group, etc.), and examples of arylene groups in A include arylene groups having 6 to 10 carbon atoms (e.g., phenylene group, torylene group, naphthylene group, etc.). Among these, the naphthylene group is a preferred example when the i-line is used as the exposure wavelength. Specific examples of imidosulfonate compounds include, but are not limited to, the compounds described in paragraphs 0092 to 0097 of International Publication No. 2015 / 064602.

[0083] Compounds having at least one cation selected from the group consisting of sulfonium cations and iodonium cations are preferably compounds in which the anion is non-nucleophilic and photodegrades to generate an organic acid with a pKa of -1 or less, and more preferably have a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, or a tris(alkylsulfonyl)methyl anion as the anion. More preferably, compounds represented by the following general formulas (ZI) or (ZII) can be listed.

[0084]

[0085] In the above general formula (ZI), R ２０１ , R ２０２ and R ２０３ Each of these independently represents an organic group. ２０１ , R ２０２ and R ２０３ The number of carbon atoms in the organic group is generally 1 to 30, preferably 1 to 20. Also, R ２０１ ~R ２０３ Two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. ２０１ ~R ２０３Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene groups, pentylene groups). － Examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, etc.

[0086] The aliphatic moiety in aliphatic sulfonate anions and aliphatic carboxylic acid anions may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

[0087] The aromatic group in aromatic sulfonic acid anions and aromatic carboxylic acid anions is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, a naphthyl group, etc.

[0088] The alkyl and aryl groups listed above may have substituents. Specific examples include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl groups (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl groups (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy groups (preferably having 5 to 20 carbon atoms), and cycloalkylalkyloxyalkyloxy groups (preferably having 8 to 20 carbon atoms). Regarding the aryl group and ring structure of each group, alkyl groups (preferably having 1 to 15 carbon atoms) can be further used as substituents.

[0089] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group, and the like.

[0090] An example of a sulfonyliimide anion is the saccharin anion.

[0091] In bis(alkylsulfonyl)imido anions and tris(alkylsulfonyl)methide anions, the alkyl group is preferably a C1-C5 alkyl group. Substituents for these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or fluorine-substituted alkyl groups being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imido anion may bond to each other to form a ring structure. This increases the acid strength. Z － Preferably, the cation contains an aromatic ring group having an alkyl group with 3 or more carbon atoms as a substituent. The alkyl group preferably has 6 or more carbon atoms, and more preferably 8 or more. The alkyl group may be linear, branched, or cyclic, and specific examples include n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-amyl, i-amyl, tert-amyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, n-octyl, and 2-ethylhexyl. Similarly, the anion is preferably a sulfonate containing an alkyl group with 6 or more carbon atoms, or a sulfonate containing an aromatic ring having an alkyl group with 3 or more carbon atoms as a substituent.

[0092] Z － Particularly preferred is the anion represented by the following general formula (AN1).

[0093]

[0094] In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. １ , R ２ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group, and when multiple Rs are present, the R is used. １ , R ２These can be the same or different. L represents a divalent linking group, and if there are multiple Ls, they can be the same or different. A represents a cyclic organic group. x represents an integer from 0 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0095] The general formula (AN1) will be explained in more detail. The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Furthermore, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom and CF ３ , C ２ F ５ , C ３ F ７ , C ４ F ９ ,CH ２ CF ３ ,CH ２ CH ２ CF ３ ,CH ２ C ２ F ５ ,CH ２ CH ２ C ２ F ５ ,CH ２ C ３ F ７ ,CH ２ CH ２ C ３ F ７ ,CH ２ C ４ F ９ ,CH ２ CH ２ C ４ F ９ These include, among others, fluorine atoms, CF ３ This is preferable. In particular, it is preferable that both Xf atoms are fluorine atoms.

[0096] R １ , R ２The alkyl group may have substituents (preferably fluorine atoms), and is preferably one with 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group with 1 to 4 carbon atoms. １ , R ２ Specific examples of alkyl groups having substituents include CF ３ , C ２ F ５ , C ３ F ７ , C ４ F ９ , C ５ F １１ , C ６ F １３ , C ７ F １５ , C ８ F １７ ,CH ２ CF ３ ,CH ２ CH ２ CF ３ ,CH ２ C ２ F ５ ,CH ２ CH ２ C ２ F ５ ,CH ２ C ３ F ７ ,CH ２ CH ２ C ３ F ７ ,CH ２ C ４ F ９ ,CH ２ CH ２ C ４ F ９ Among them, CF ３ This is preferable. １ , R ２ Preferably, it is a fluorine atom or CF ３ That is the case.

[0097] x is preferably 0 to 10, more preferably 0 to 2. y is preferably 0 to 8, more preferably 0 to 6. z is preferably 0 to 5, more preferably 0 to 3. The divalent linking group of L is not particularly limited and can be -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ２Examples include alkylene groups, cycloalkylene groups, alkenylene groups, or linked groups formed by linking multiple thereof, with linked groups having a total of 12 or fewer carbon atoms being preferred. Among these, -COO-, -OCO-, -CO-, and -O- are preferred, and -COO- and -OCO- are more preferred.

[0098] The cyclic organic group A is not particularly limited as long as it has a cyclic structure, and examples include alicyclic groups, aryl groups, and heterocyclic groups (including not only aromatic but also non-aromatic ones). Alicyclic groups may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups, and polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups are preferred. Among these, alicyclic groups with a bulky structure having 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred from the viewpoint of improving MEEF because they can suppress diffusion in the film during the post-exposure heating process. Examples of aryl groups include benzene rings, naphthalene rings, phenanthrene rings, and anthracene rings. Examples of heterocyclic groups include those derived from furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Among these, those derived from furan rings, thiophene rings, and pyridine rings are preferred.

[0099] The above-mentioned cyclic organic group may have substituents, and examples of such substituents include linear or branched alkyl groups (which may be linear, branched, or cyclic, and preferably have 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, and preferably have 3 to 20 carbon atoms), aryl groups (preferably have 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, sulfonic acid ester groups, and the like. The carbon atoms constituting the cyclic organic group (carbon atoms that contribute to ring formation) may be carbonyl carbons.

[0100] R ２０１ , R ２０２ and R２０３ Examples of organic groups include aryl groups, alkyl groups, and cycloalkyl groups. ２０１ , R ２０２ and R ２０３ It is preferable that at least one of these is an aryl group, and more preferably that all three are aryl groups. In addition to phenyl and naphthyl groups, heteroaryl groups such as indole and pyrrole residues are also possible as aryl groups. ２０１ ~R ２０３ Preferably, the alkyl and cycloalkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms. More preferably, alkyl groups include methyl, ethyl, n-propyl, i-propyl, and n-butyl groups. More preferably, cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups. These groups may further have substituents. Examples of substituents include, but are not limited to, nitro, halogen atoms such as fluorine, carboxy, hydroxyl, amino, cyano, alkoxy (preferably C1 to C15), cycloalkyl groups (preferably C3 to C15), aryl groups (preferably C6 to C14), alkoxycarbonyl groups (preferably C2 to C7), acyl groups (preferably C2 to C12), and alkoxycarbonyloxy groups (preferably C2 to C7).

[0101] The divalent linking groups of Za include alkylene groups, arylene groups, carbonyl groups, sulfonyl groups, carbonyloxy groups, carbonylamino groups, sulfonylamide groups, ether bonds, thioether bonds, amino groups, disulfide groups, and -(CH ２ ) ｎ -CO-, -(CH ２ ) ｎ -SO ２ Examples include -, -CH=CH-, aminocarbonylamino group, aminosulfonylamino group, etc. (n is an integer from 1 to 3).

[0102] Note R ２０１ , R２０２ and R ２０３ In cases where at least one of the groups is not an aryl group, preferred structures include cationic structures such as those described in paragraphs 0046 to 0048 of Japanese Patent Publication No. 2004-233661, paragraphs 0040 to 0046 of Japanese Patent Publication No. 2003-35948, the compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003 / 0224288A1, and the compounds exemplified as formulas (IA-1) to (IA-54) and (IB-1) to (IB-24) in U.S. Patent Application Publication No. 2003 / 0077540A1.

[0103] In general formula (ZII), R ２０４ ~R ２０５ R represents an aryl group. ２０４ ~R ２０５ As for the aryl group, the R in the aforementioned compound (ZI) ２０１ ~R ２０３ This is similar to the aryl group described as an aryl group. ２０４ ~R ２０５ The aryl group may have substituents. These substituents may also be R in the aforementioned compound (ZI). ２０１ ~R ２０３ Examples of aryl groups that may be present include:

[0104] Specific examples of compounds having at least one cation selected from the group consisting of sulfonium cations and iodonium cations include, but are not limited to, the compounds described in paragraphs 0128-0133 of International Publication No. 2015 / 064602.

[0105] The content of the photoacid generator is preferably 0.1 to 20% by mass, and more preferably 0.5 to 18% by mass, relative to the total solid content of the chemically amplified polarity-converting negative composition. The photoacid generator may be contained alone or in combination of two or more types. When the chemically amplified polarity-converting negative composition contains two or more types of photoacid generators, it is preferable that their total content be within the above range.

[0106] (Acid Diffusion Control Agent) A chemically amplified polarity-converting negative composition may contain an acid diffusion control agent. The acid diffusion control agent is a compound that acts as a quencher to trap the acid generated from the photoacid generator and can control the diffusion of the acid. Examples of acid diffusion control agents include basic compounds. Examples of acid diffusion control agents include the compounds described in paragraphs

[0315] to

[0337] of Japanese Patent Application Publication No. 2023-184542 and the compounds described in paragraphs

[0140] to

[0144] of Japanese Patent Application Publication No. 2013-11833 (amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds, etc.), the details of which are incorporated herein by reference.

[0107] The content of the acid diffusion control agent is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass, relative to the total solid content of the chemically amplified polarity-converting negative composition. The acid diffusion control agent may be contained alone or in combination of two or more types. When the chemically amplified polarity-converting negative composition contains two or more types of acid diffusion control agents, it is preferable that their total content be within the above range.

[0108] (Other Additives) Chemically amplified polarity-converting negative compositions may contain components other than those listed above (hereinafter also referred to as "other additives"). Examples of such additives include crosslinking agents, hydrophobic resins (preferably different resins from resin (B)), surfactants, onium carboxylates, etc. For other additives, refer to paragraphs

[0204] to

[0332] of International Publication No. 2016 / 208300, which are incorporated herein by reference.

[0109] On the other hand, in the present invention, the photosensitive resin composition may be a non-chemically amplified polarity-converting negative type composition. Examples of non-chemically amplified polarity-converting negative type compositions include a photosensitive resin composition containing a resin that generates acidic groups (e.g., carboxylic acids, sulfonic acids, etc.) upon exposure and a compound that interacts with the acidic groups (e.g., amine compounds, etc.).

[0110] (Substrate) The substrate to which the photosensitive resin composition is applied is a component that supports the redistribution layer obtained by the redistribution layer formation process. Examples of substrates include inorganic substrates, resin substrates, and composite substrates thereof. Specific examples of materials constituting the inorganic substrate include glass, quartz, silicone, and silicon nitride. The inorganic substrate may also be a composite substrate obtained by depositing molybdenum, titanium, aluminum, or copper onto a substrate containing any of these materials. Specific examples of materials constituting a resin substrate include synthetic resins such as polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene and other fluororesins, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins, cyanate resins, crosslinked fumarate diesters, cyclic polyolefins, aromatic ethers, maleimide-olefins, cellulose, and episulfide compounds. A substrate composed of such a synthetic resin may, for example, take the form of a multilayer laminated structure such as a thin-film transistor (TFT).

[0111] In the present invention, the above-mentioned semiconductor element may be used as a substrate. Similarly, a package substrate may be used as a substrate. Hereinafter, in this specification, a package substrate is a substrate used when mounting a semiconductor element on a motherboard or the like.

[0112] <Step 2: Formation of the Upper Layer Film> Step 2 is the process of forming an upper layer film on the photosensitive resin composition layer formed in Step 1, in which exposure increases the transmittance to the exposure wavelength. Here, "increased transmittance to the exposure wavelength due to exposure" refers to the characteristic that the exposed area is altered by pattern exposure in Step 3, described later, and has a higher transmittance to the exposure wavelength compared to the unexposed area (i.e., the upper layer film before exposure). The transmittance to the exposure wavelength can be measured using a known transmittance meter (for example, the V-700 series manufactured by JASCO Corporation), but the transmittance to the exposure wavelength in the unexposed area is the value measured without exposure treatment on the measurement sample, and the transmittance to the exposure wavelength in the exposed area is measured with a light source of the exposure wavelength at 800 mJ / cm² on the measurement sample. ２ This refers to the value measured after exposure processing with the specified exposure level.

[0113] Figure 1B is a schematic cross-sectional view illustrating step 2, showing a cross-section along the thickness direction of the substrate 1, the photosensitive resin composition layer 2, and the upper film 3. In the example in Figure 1B, an example is shown in which the upper film 3 is formed in contact with the photosensitive resin composition layer 2, but the example is not limited to this, and the upper film 3 may be formed on the photosensitive resin composition layer 2 via other layers (limited to layers that are removed by the developer used in step 4, which will be described later).

[0114] In the present invention, for better dimensional uniformity of the pattern, the upper layer is preferably a layer whose transmittance increases by 10% or more with respect to the exposure wavelength upon exposure, more preferably by 20% or more, even more preferably by 30% or more, and particularly preferably by 40% or more. The upper limit of the difference in transmittance is not particularly limited, but is generally 90% or less.

[0115] The upper layer is not particularly limited as long as it is a layer whose transmittance with respect to the exposure wavelength increases upon exposure, for example, a layer containing a photocatalytic material, and conventionally known contrast enhancement layers (CELs) can be appropriately adopted. Here, examples of photocatalytic materials include photocatalytic materials such as nitrone and diazonium salts (for example, compounds described in Japanese Patent Publication No. 62-40697, M. Sasano et al., SPIE Symp. Proc., 631, 321 (1986)), and compounds described in paragraphs

[0012] to

[0017] of Japanese Patent Application Publication No. 2010-230995, and these descriptions are incorporated herein by reference.

[0116] The method for forming the upper layer film is not particularly limited. For example, a method can be used in which a composition containing the above-mentioned photodecolorizing material (hereinafter also referred to as "upper layer film forming composition") is applied to a photosensitive resin composition layer and dried. Here, coating is preferred as the means for applying the upper layer film forming composition to the photosensitive resin composition layer, and specific examples of this are the same as those for applying the photosensitive resin composition to a substrate.

[0117] The composition for forming the upper layer film preferably contains a resin from the viewpoint of workability during upper layer film formation. Examples of resins include those described in paragraphs

[0018] to

[0043] of Japanese Patent Application Publication No. 2010-230995, which are incorporated herein by reference.

[0118] From the viewpoint of workability during upper film formation, the composition for forming the upper film preferably contains a solvent, and more preferably an organic solvent. As the organic solvent, at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGME), propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl methoxypropionate, cyclopentanone, cyclohexanone (CHN), γ-butyrolactone, diisoamyl ether, butyl acetate (nBA), isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, n-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate (PC), sulfolane, cycloheptanone, 1-hexanol, decane, and 2-heptanone is preferred.

[0119] The upper film-forming composition may, if necessary, contain small amounts of various additives such as photosensitive agents, dissolution inhibitors, other resins, surfactants, stabilizers, and dyes.

[0120] In the present invention, step 2 may include a heat treatment (soft bake) in which the upper film-forming composition applied to the photosensitive resin composition layer is heated. This removes components such as solvents from the upper film-forming composition applied to the photosensitive resin composition layer. The heating temperature in the heat treatment is preferably 50 to 150°C. Heating may also be performed under reduced pressure. The heating time is preferably 30 seconds to 3 minutes.

[0121] <Step 3: Pattern Exposure> Step 3 is a step in which the laminate of the photosensitive resin composition layer and the upper film is pattern exposed. Figure 1C is a schematic cross-sectional view to explain Step 3, and is a schematic diagram showing how a portion 3a with increased transmittance in the upper film 3 and an exposed portion 2a in the photosensitive resin composition layer are created by pattern exposure from the position of the arrow.

[0122] One method of pattern exposure is to selectively expose the photosensitive resin composition layer and the upper film. Selective exposure means exposing only a portion of the photosensitive resin composition layer and the upper film. By selective exposure, exposed areas 2a and unexposed areas 2b are formed in the photosensitive resin composition layer, and exposed areas (parts with increased transmittance) 3a and unexposed areas 3b are formed in the upper film.

[0123] The exposure amount is not particularly limited as long as it can cure the photosensitive resin composition, but for example, it can be 50 to 10,000 mJ / cm² in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0124] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0125] In relation to the light source, the exposure wavelength can be (1) semiconductor lasers (e.g., wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths of g, h, and i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２ Examples include excimer lasers (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beams, and (7) YAG lasers with second harmonics of 532 nm and third harmonics of 355 nm. For composition A1, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the photosensitive resin composition layer is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0126] In the present invention, from the viewpoint of achieving both resolution and pattern shape, the exposure wavelength for pattern exposure is preferably 350 to 410 nm, and more preferably 365 nm (i.e., i-line).

[0127] (Post-exposure heat treatment) Step 3 may include a post-exposure heat treatment (post-exposure bake) in which the photosensitive resin composition layer is heated after pattern exposure. The post-exposure heat treatment can be performed after the exposure treatment and before the development treatment. The heating temperature in the post-exposure heat treatment is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heat treatment is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heat treatment is preferably 1 to 12°C / min from the starting temperature to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heat treatment is not particularly limited, and known examples include hot plates, ovens, and infrared heaters. It is also preferable to perform the heating in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, and argon.

[0128] <Step 4: Formation of Negative Pattern> Step 4 is a process in which the unexposed portion of the photosensitive resin composition layer and the upper layer (the entire upper layer including both the exposed and unexposed portions) of the laminate after pattern exposure are removed with a developer containing an organic solvent to obtain a negative pattern consisting of the exposed portion of the photosensitive resin composition layer. Figure 1D is a schematic cross-sectional view to explain Step 4, and is a schematic diagram showing the state in which the unexposed portion 2b of the photosensitive resin composition layer and the upper layer 3 have been removed, and a negative pattern consisting of the exposed portion 2a of the photosensitive resin composition layer has been formed.

[0129] Examples of organic solvents included in the developer include compounds described in paragraph

[0387] of International Publication No. 2021 / 112189, which are incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, while suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide. The organic solvents included in the developer can be used individually or in combination of two or more.

[0130] In this invention, it is preferable that the SP value of the developer is greater than the SP value of the solvent used to form the upper layer film, for the reason that the dimensional uniformity of the pattern is better, and that the SP value is 1.0 MPa greater than the SP value of the solvent used to form the upper layer film. １／２ A value greater than the above is preferable. Here, the SP value is the energy δd(MPa) due to the intermolecular dispersion force. １／２ ), energy δp (MPa) due to intermolecular dipole interactions １／２ ), and the energy δh (MPa) due to intermolecular hydrogen bonding. １／２ It is composed of these three energy vectors, and the SP value is obtained as the sum of these three energy vectors.

[0131] The SP values ​​of many substances have been determined by Hansen and his research successors, and are documented in the Polymer Handbook (fourth edition), VII-698-711, and in the Industrial Solvents Handbook by Wesley L. Archer. Furthermore, the SP value can be calculated using software such as Hansen Solubility Parameter in Practice (HSPiP, Charles M. Hansen, URL: http: / / www.hansen-solubil.com / ).

[0132] The SP values ​​described in this embodiment were calculated using the 5th Edition 5.4.01 of "HSPiP," a database-equipped calculation software developed and sold by the Hansen Group, by inputting the chemical structural formula of the compound.

[0133] Furthermore, in the present invention, from the viewpoint of improving resolution and further improving the dimensional uniformity of the pattern, it is preferable that the developer contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene.

[0134] The content of organic solvent in the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the developer. Alternatively, the above content may be 100% by mass.

[0135] The developing solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0136] (Rinsing process) Step 4 may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after the negative pattern has been obtained. Alternatively, methods such as supplying the rinsing solution before the developer solution remaining on the negative pattern has completely dried may be employed.

[0137] There are no particular restrictions on the method of supplying the rinse solution. These include immersing the negative pattern in the rinse solution, supplying the rinse solution to the negative pattern by filling it with liquid, supplying the rinse solution to the negative pattern with a shower, and continuously supplying the rinse solution onto the negative pattern using means such as a straight nozzle. The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinse solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0138] As a rinsing solution, for example, a solvent different from the solvent contained in the developer (e.g., water, or an organic solvent different from the organic solvent contained in the developer) can be used. Examples of organic solvents different from the organic solvent contained in the developer include organic solvents similar to those exemplified above as organic solvents contained in the developer. Among these, an organic solvent with lower pattern solubility than the organic solvent contained in the developer is preferred.

[0139] If the rinsing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the organic solvent may be 100% by mass relative to the total mass of the rinsing solution.

[0140] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0141] (Heat treatment) Step 4 may include a heat treatment (post-bake) in which the obtained negative pattern is heated. If a rinsing treatment is performed, the heat treatment may be performed on the negative pattern after rinsing. During the heat treatment, the resin such as the polyimide precursor is cyclized to become a resin such as polyimide. Crosslinking of unreacted crosslinkable groups also proceeds.

[0142] The heating temperature (maximum heating temperature) in the heat treatment is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, particularly preferably 160 to 250°C, and most preferably 160 to 230°C. For the heat treatment, reference can be given to paragraphs

[0326] to

[0332] of International Publication No. 2023 / 190064, which are incorporated herein by reference.

[0143] <Step 5: Formation of the conductive part> Step 5 is a step in which the conductive part is formed using the negative pattern described above as a mold by plating. Figure 1E is a schematic cross-sectional view to explain step 5, and is a schematic diagram showing how the metal layer 4 is formed using the negative pattern as a mold.

[0144] Known plating methods include electroplating and electroless plating. Below is an example of a method for forming a metal layer by plating. First, a seed layer (for example, a Ti barrier layer made of titanium) is provided in the region including the surface of the recess (exposed area removed by the developer) created by the formation of the negative pattern by a method such as sputtering. Next, a metal layer is formed by performing electroplating (for example, electrolytic copper plating) on ​​the seed layer. Before performing electroplating, the seed layer may be pretreated by sulfuric acid treatment and water washing.

[0145] The materials constituting the metal layer are not particularly limited, but include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Among these, copper or aluminum is preferred, and copper is more preferred.

[0146] <Other Processes> If the substrate is not a package substrate, the redistribution layer formation process may include a package substrate connection process that connects the package substrate and the redistribution layer. It is preferable that the package substrate is formed on the side opposite to the side on which the semiconductor elements are formed in the redistribution layer. Known methods can be used to connect the package substrate and the redistribution layer, and specifically, methods using bonding wires or solder balls can be used. This electrically connects the package substrate and the redistribution layer.

[0147] [Composition for forming an upper layer film] The upper layer film formation composition of the present invention is a composition used in the semiconductor device manufacturing method of the present invention described above, and contains the photodecolorizing material described above. Furthermore, as explained in step 2 of the redistribution layer formation process described above, the upper layer film formation composition of the present invention may also contain the resin, solvent, photosensitive agent, dissolution inhibitor, other resin, surfactant, stabilizer, dye, etc., as described above, from the viewpoint of workability during upper layer film formation.

[0148] [Photosensitive Resin Composition] The photosensitive resin composition used in the method for manufacturing the semiconductor device of the present invention described above (hereinafter also formally abbreviated as "the photosensitive resin composition of the present invention") is not particularly limited as long as it can form a photosensitive resin composition layer in which the dissolution rate in an organic solvent decreases upon exposure, as explained in step 1 of the redistribution layer formation process described above. Furthermore, as described above, it is preferable that the photosensitive resin composition of the present invention contains at least one resin (hereinafter abbreviated as "resin (A)") selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Furthermore, the photosensitive resin composition of the present invention may be in the form of a film or a liquid, but it is preferable that it be in the form of a liquid. The components that may be included in the photosensitive resin composition of the present invention will be described in detail below.

[0149] [Resin (A)] Resin (A) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Here, polyimide precursor refers to a resin that undergoes a change in chemical structure to become polyimide upon external stimuli, preferably a resin that undergoes a change in chemical structure to become polyimide upon heat, and more preferably a resin that undergoes a ring-closing reaction upon heat to form a ring structure to become polyimide. Polyimide refers to a resin having repeating units containing imide groups in its molecular chain, and it is preferable that the resin has repeating units containing imide ring structures in its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide groups in its main chain, and more preferably a resin having repeating units containing imide ring structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. In this specification, an imide group refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, an imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above imide as ring member atoms. The imide ring structure is preferably a five-membered ring. Polyimides may also be so-called polyamideimides, which have an amide group in the molecular chain in addition to an imide group. In this specification, an amide group refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0150] The photosensitive resin composition of the present invention preferably contains polyimide or a polyimide precursor as resin (A). Resin (A) preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If resin (A) has radical polymerizable groups, the photosensitive resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a photosensitive agent may be included as needed. Such a photosensitive resin composition of the present invention is a crosslinking negative type composition. Resin (A) may also have polarity conversion groups such as acid-degradable groups. If resin (A) has polarity conversion groups, the photosensitive resin composition of the present invention preferably contains a photoacid generator. Such a photosensitive resin composition of the present invention can also be a chemically amplified polarity conversion negative type composition.

[0151] <Polyimide Precursor> The polyimide precursor used in the present invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2).

[0152]

[0153] In formula (2), A １ and A ２ Each of these is independently an oxygen atom or -NR ｚ - represents R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ｚ represents a hydrogen atom or a monovalent organic group.

[0154] A in equation (2) １ and A ２ Each of these is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. １１１ R represents a divalent organic group. １１１ It is preferable that the base is one of the bases described in paragraphs

[0042] to

[0053] of Japanese Patent Publication No. 2023-003421.

[0155] Also, R １１１ From the viewpoint of i-ray transmittance, a divalent organic group represented by formula (51) or formula (61) below is preferred, and in particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

[0156]

[0157] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0158]

[0159] In formula (61), R ５８ and R ５９ Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0160] R in equation (2) １１５ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure.

[0161]

[0162] In formula (5), R １１２ The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ It is more preferable that the group is selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0163] R １１５ Preferably, the tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs

[0055] to

[0057] of Japanese Patent Application Publication No. 2023-003421 is preferred.

[0164] In equation (2), R １１１ and R １１５ It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0165] R in equation (2) １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat and radicals, and radical polymerizable groups are preferred. Examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0166]

[0167] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -, or a polyalkylene oxy group is preferred, and an alkylene group such as an ethylene group and a propylene group, -CH ２ CH(OH)CH ２-, cyclohexyl groups, or polyalkylene oxy groups are more preferred, and alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group means a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be a random arrangement, an arrangement with blocks, or an arrangement with a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, or halogen atoms. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0168] In equation (2), R １１３If R is a hydrogen atom, １１４ When is a hydrogen atom, the polyimide precursor may form a pair salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0169] In equation (2), R １１３ and R １１４ At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, or tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Examples of acid-degradable groups include tert-butoxycarbonyl groups, isopropoxycarbonyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, ethoxyethyl groups, methoxyethyl groups, ethoxymethyl groups, trimethylsilyl groups, tert-butoxycarbonylmethyl groups, and trimethylsilyl ether groups. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0170] The polyimide precursor may also preferably contain fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less, based on the total mass of the polyimide precursor.

[0171] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0172] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to broaden the exposure latitude.

[0173] Formula (2-A)

[0174] In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ Each of these independently represents a divalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R １１３ and R １１４ Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0175] A １ A ２ , R １１１ , R １１３ and R １１４ Each of these independently corresponds to A in equation (2). １ A ２ , R １１１ , R １１３ and R １１４ This is synonymous with the following, and the preferred range is also similar. １１２ R in equation (5) is １１２ This is synonymous with the same thing, and the preferred range is also similar.

[0176] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2), the polyimide precursor may also contain other types of repeating units.

[0177] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more relative to the total number of repeating units. The above content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0178] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 300,000, more preferably 5,000 to 100,000, even more preferably 10,000 to 50,000, and particularly preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When the photosensitive resin composition of the present invention contains multiple types of polyimide precursors as resin (A), it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0179] <Polyimide> The polyimide used in the present invention is preferably a polyimide that is soluble in a developer mainly composed of an organic solvent. From the viewpoint of film strength and insulating properties of the resulting photosensitive resin composition layer, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0180] (Fluorine atoms) From the viewpoint of the film strength of the resulting photosensitive resin composition layer, it is also preferable that the polyimide has fluorine atoms. Fluorine atoms are, for example, in the repeating unit represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit represented by formula (4) described later, R １３２ , or R in the repeating unit represented by formula (4) described later. １３１ It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0181] (Silicon atoms) From the viewpoint of the film strength of the resulting photosensitive resin composition layer, it is also preferable that the polyimide has silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit represented by formula (4) described later, R １３１ It is more preferable that the silicon atoms or the organically modified (poly)siloxane structure described later be included. The silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0182] (Ethylene-unsaturated bond) From the viewpoint of the film strength of the resulting photosensitive resin composition layer, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in the side chains, but it is preferable that it has one in the side chains. It is preferable that the above ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３２ or R １３１ Preferably, it is included in R １３２ or R １３１It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in R １３１ It is more preferable that the group contains an ethylenically unsaturated bond. Examples of groups containing an ethylenically unsaturated bond include vinyl groups, allyl groups, and vinylphenyl groups, which have a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0183]

[0184] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0185] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２ The characters represent -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 or 3 carbon atoms; the repeating number of the alkylene oxy group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0186] Among these, R ２１ Preferably, the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1).

[0187]

[0188] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). ２１ This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), a preferred embodiment of L is an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, as shown in formula (IV) R ２１ The preferred embodiment is the same as that of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * is the same as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0189] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0190] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0191] (Polymerizable groups other than those having ethylenically unsaturated bonds) Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. A polymerizable group other than those having ethylenically unsaturated bonds is, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in the following. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0192] (Polarity-changing group) Polyimide may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimide is R in formula (2) above. １１３ and R １１４ The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity-converting group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found in the ends of polyimides, etc.

[0193] (Acid Value) The acid value of polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. As for the acid group contained in polyimide, from the viewpoint of achieving both storage stability and developability, an acid group with a pKa of 0 to 10 is preferred, and an acid group with a pKa of 3 to 8 is more preferred. pKa is the equilibrium constant Ka, expressed as its negative common logarithm pKa, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The value of pKa may refer to the value published in "Revised 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. When the acid group is a polyhydric acid such as phosphoric acid, the above pKa is the first dissociation constant. The polyimide preferably contains at least one such acid group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0194] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4).

[0195] In formula (4), R １３１ represents a divalent organic group, R １３２ R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below.

[0196] Formula (4-1)

[0197] In formula (4-1), R １３３ is a polymerizable group, and the other groups are equivalent to formula (4).

[0198] Formula (4-2)

[0199] In formula (4-2), R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is a monovalent organic group, and the other group is equivalent to formula (4).

[0200] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or polymerizable groups other than those having the ethylenically unsaturated bond described above. １３１ R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is １１１ Similar examples are given, and the preferred range is also similar. １３１ Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic diamines, cyclic aliphatic diamines, and aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. １１１ Examples include:

[0201] R １３１ It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, in order to more effectively suppress the occurrence of warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0202] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0203] R １３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５Similar examples are given, and the preferred range is also similar. For example, R １１５ The four bonders of the tetravalent organic group, as exemplified, bond with the four -C(=O)- parts in formula (4) to form a fused ring.

[0204] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. １３２ A specific example of this is R in formula (2) of the polyimide precursor. １１５ Examples include: From the viewpoint of the strength of the photosensitive resin composition layer, R １３２ Preferably, the aromatic diamine residue has one to four aromatic rings.

[0205] R １３１ and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１ Preferably, R is 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, or the above (DA-1) to (DA-18). １３２ Of these, (DAA-1) to (DAA-5) above are more preferable.

[0206] It is also preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less, based on the total mass of the polyimide.

[0207] To improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0208] (Imidization rate (ring closure rate)) The imidization rate (also called the "ring closure rate") of polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of film strength, insulating properties, etc. of the resulting photosensitive resin composition layer. The upper limit of the above imidization rate is not particularly limited and may be 100% or less. The above imidization rate is measured, for example, by the following method: The infrared absorption spectrum of the polyimide is measured, and the absorption peak originating from the imide structure is 1377 cm⁻¹. －１ The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. －１ Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula: Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0209] Polyimide is a material in which all repeating units are R １３１ and R １３２ The combination of R may include the repeating unit represented by the above formula (4), which is the same. １３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of elements. In addition to the repeating units represented by formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

[0210] Polyimides can be synthesized by obtaining a polyimide precursor using methods such as: reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting a tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing this precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0211] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 300,000, more preferably 5,000 to 100,000, even more preferably 10,000 to 50,000, and particularly preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the cured film can be improved. To obtain a film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the photosensitive resin composition of the present invention contains multiple types of polyimide as resin (A), it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the above multiple types of polyimide are treated as a single resin are each within the above range.

[0212] <Polybenzoxazole precursors> Examples of polybenzoxazole precursors include the compounds described in paragraphs

[0073] to

[0095] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0213] <Polybenzoxazoles> Examples of polybenzoxazoles include the compounds described in paragraphs

[0101] to

[0108] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0214] <Polyamide-imide precursors> Examples of polyamide-imide precursors include the compounds described in paragraphs

[0104] to

[0119] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0215] <Polyamideimides> Examples of polyamideimides include the compounds described in paragraphs

[0125] to

[0138] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0216] <Method for producing polyimide precursors, etc.> Polyimide precursors, etc. are produced, for example, by the method described in paragraphs

[0134] to

[0136] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0217] <Content> The content of resin (A) in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. Furthermore, the content of resin (A) in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, particularly preferably 97% by mass or less, and particularly preferably 95% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of resin (A) or may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above range.

[0218] The photosensitive resin composition of the present invention may also preferably contain at least two types of resins. Specifically, the photosensitive resin composition of the present invention may contain a total of two or more types of resin (A) and other resins described later, or it may contain two or more types of resin (A), but it is preferable to contain two or more types of resin (A). When the photosensitive resin composition of the present invention contains two or more types of resin (A), for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above) １１５ Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0219] [Other Resins] The photosensitive resin composition of the present invention may contain the resin (A) described above and other resins different from resin (A) (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, a photosensitive resin composition of the present invention with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable compound with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to the photosensitive resin composition of the present invention, the coatability of the photosensitive resin composition of the present invention, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0220] If the photosensitive resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, particularly preferably 5% by mass or more, and most preferably 10% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. In the photosensitive resin composition of the present invention, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention. In one preferred embodiment of the photosensitive resin composition of the present invention, the content of other resins is also low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 1% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention. The lower limit of the above content is not particularly limited, and it is sufficient if it is 0% by mass or more. The photosensitive resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more resins, it is preferable that the total amount is within the above range.

[0221] [Polymerizable Compounds] The photosensitive resin composition of the present invention preferably contains polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0222] <Radical Crosslinking Agent> The photosensitive resin composition of the present invention (particularly the crosslinked negative type composition) preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, or vinylphenyl group is preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0223] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 is even more preferred. From the viewpoint of the film strength of the resulting pattern (cured product), the photosensitive resin composition of the present invention may also preferably contain a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0224] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0225] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), or their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys are also suitably used. Dehydration condensation reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitably used. Furthermore, substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. For specific examples, refer to paragraphs

[0113] to

[0122] of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0226] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph

[0203] of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0227] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs

[0204] to

[0208] of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0228] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0229] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0230] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0231] The radical crosslinking agent may be a radical crosslinking agent having acidic groups such as carboxyl groups and phosphate groups. As a radical crosslinking agent having acidic groups, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group is more preferred. As a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, a compound in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is preferred. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0232] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0233] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs

[0133] to

[0143] of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0234] As radical crosslinking agents, bifunctional methacrylates or acrylates are preferred from the viewpoint of pattern resolution and film stretchability. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1 Examples include ,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, difunctional acrylates having urethane bonds, and difunctional methacrylates having urethane bonds. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is about 200. As a radical crosslinking agent, a monofunctional radical crosslinking agent is preferred from the viewpoint of suppressing warping of the pattern (cured product).Examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As monofunctional radical crosslinking agents, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or multifunctional radical crosslinking agents include diallyl phthalate and allyl compounds such as triallyl trimellitate.

[0235] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0236] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0237] <Other Crosslinking Agents> The photosensitive resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon photosensitivity with a photoacid generator or photobase generator, and more preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. As the acid or base, it is preferable that the acid or base is generated from the photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs

[0179] to

[0207] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0238] If other crosslinking agents are included, the content of the other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one other crosslinking agent or two or more other crosslinking agents. If two or more other crosslinking agents are included, it is preferable that their total content is within the above range.

[0239] [Polymerization Initiator] The photosensitive resin composition of the present invention (particularly the crosslinked negative type composition) preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, an activator that reacts with the photoexcited photosensitizer to generate active radicals may also be used.

[0240] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm).－１ ・cm －１ It is preferable to include at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0241] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and compounds having a trihalomethyl group), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, refer to paragraphs

[0165] to

[0182] of Japanese Patent Application Publication No. 2016-027357 and paragraphs

[0138] to

[0151] of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs

[0065] to

[0111] of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0242] Examples of ketone compounds include those described in paragraph

[0087] of Japanese Patent Application Laid-Open No. 2015-087611, the content of which is incorporated herein by reference. As commercial products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0243] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferred as the photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the content of which is incorporated herein by reference.

[0244] As α-hydroxyketone-based initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0245] As α-aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0246] As aminoacetophenone-based initiators, acylphosphine oxide-based initiators, and metallocene compounds, for example, the compounds described in paragraphs

[0161] to

[0163] of International Publication No. WO 2021 / 112189 can also be preferably used. The content of the above publication is incorporated herein by reference.

[0247] As a photoradical polymerization initiator, an oxime compound is preferable. Use of an oxime compound makes it possible to more effectively improve exposure latitude. Oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also function as a photo-curing accelerator.

[0248] Examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Laid-Open No. 2000-066385, compounds described in Japanese National Publication of International Patent Application No. 2004-534797, compounds described in Japanese Patent Application Laid-Open No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application Laid-Open No. 2017-198865, compounds described in paragraphs

[0025] to

[0038] of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein.

[0249] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, or 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound used as a photoradical polymerization initiator has a >C=N-O-C(=O)- linking group in its molecule.

[0250]

[0251] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0252]

[0253] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs

[0169] to

[0171] of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs

[0208] to

[0210] of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0254] In addition, compounds described in paragraphs

[0113] to

[0117] of Japanese Patent Application Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated herein by reference.

[0255] When the photosensitive resin composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of polymerization initiator or may contain two or more types. When two or more types are included, it is preferable that the total amount be within the above range. Note that since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0256] [Photosensitive Agent] The photosensitive resin composition of the present invention (particularly the crosslinked negative type composition) may contain a photosensitive agent. The photosensitive agent absorbs specific active radiation and enters an electronically excited state. The photosensitive agent in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and decompose, generating radicals, acids, or bases. Examples of photosensitive agents include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyrane, and indigo.Examples of photosensitive agents include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, refer to paragraphs

[0161] to

[0163] of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0257] When the photosensitive resin composition of the present invention contains a photosensitive agent, the content of the photosensitive agent is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of photosensitive agent or may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0258] [Base Generator] The photosensitive resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, if the photosensitive resin composition of the present invention contains a precursor of a cyclized resin, it is preferable that the photosensitive resin composition of the present invention contains a base generator. By containing a thermal base generator in the photosensitive resin composition of the present invention, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and good performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. Known base generators can be used as the base generator. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs

[0249] to

[0277] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0259] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0260] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs

[0148] to

[0163] of International Publication No. 2018 / 038002 and the compounds described in paragraphs

[0280] to

[0281] of International Publication No. 2022 / 145355, the contents of which are incorporated herein by reference.

[0261] When the photosensitive resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the photosensitive resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. The photosensitive resin composition of the present invention may contain only one type of base generating agent, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0262] [Photoacid Generator] The photosensitive resin composition of the present invention may contain a photoacid generator. Examples of photoacid generators include those described in the above-mentioned chemical amplification type polarity conversion negative composition, and among these, nonionic photoacid generators are preferred.

[0263] [Solvent] The photosensitive resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0264] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl propionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate).

[0265] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0266] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0267] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, as well as cyclic terpenes such as limonene.

[0268] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0269] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0270] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0271] Suitable alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0272] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0273] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate, is more preferred.

[0274] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0275] [Metal Adhesion Modifying Agent] The photosensitive resin composition of the present invention preferably contains a metal adhesion modifying agent from the viewpoint of improving adhesion to metal materials used in electrodes and wiring, etc. Examples of metal adhesion modifying agents include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0276] <Silane Coupling Agent> Examples of the silane coupling agent include the compounds described in paragraph

[0316] of International Publication No. WO 2021 / 112189, and the compounds described in paragraphs

[0067] to

[0078] of Japanese Patent Laid-Open No. 2018-173573, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs

[0050] to

[0058] of Japanese Patent Laid-Open No. 2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formulas, Me represents a methyl group, and Et represents an ethyl group. In addition, examples of the following R include a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected according to the elimination temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferable from the viewpoint of setting the elimination temperature to 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

[0277]

[0278] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-( Examples include aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0279]

[0280] In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc. Vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups are preferred, vinylphenyl groups or (meth)acryloyloxy groups are more preferred, and (meth)acryloyloxy groups are even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercial products can be used as such oligomer-type compounds, and an example of a commercial product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0281] Other metal adhesion modifiers that can be used include the compounds described in paragraphs

[0046] to

[0049] of Japanese Patent Application Publication No. 2014-186186, and the sulfide compounds described in paragraphs

[0032] to

[0043] of Japanese Patent Application Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0282] When the photosensitive resin composition of the present invention contains a metal adhesion modifier, the content of the metal adhesion modifier is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of resin (A). A content above the lower limit provides good adhesion between the pattern and the metal layer, while a content below the upper limit provides good heat resistance and mechanical properties of the pattern. The photosensitive resin composition of the present invention may contain only one type of metal adhesion modifier, or it may contain two or more types. When containing two or more types, it is preferable that the total amount falls within the above range.

[0283] [Migration Inhibitor] The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the photosensitive resin composition of the present invention is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0284] There are no particular limitations on the migration inhibitors, but examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, or tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0285] As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions can also be used.

[0286] Other migration inhibitors that can be used include the rust inhibitor described in paragraph

[0094] of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs

[0073] to

[0076] of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph

[0052] of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs

[0114] ,

[0116] and

[0118] of Japanese Patent Publication No. 2012-194520, the compounds described in paragraph

[0166] of International Publication No. 2015 / 199219, and the like, which are incorporated herein by reference.

[0287] Specific examples of migration inhibitors include the following compounds.

[0288]

[0289] When the photosensitive resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the photosensitive resin composition. The photosensitive resin composition of the present invention may contain only one type of migration inhibitor or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0290] [Polymerization Inhibitor] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0291] Specific examples of polymerization inhibitors include the compounds described in paragraph

[0310] of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide. This information is incorporated herein by reference.

[0292] If the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one polymerization inhibitor or two or more. If it contains two or more, it is preferable that the total amount is within the above range.

[0293] [Light Absorber] The photosensitive resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs

[0159] to

[0183] of International Publication No. 2022 / 202647 and the compounds described in paragraphs

[0088] to

[0108] of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0294] When the photosensitive resin composition of the present invention contains a light absorber, the content of the light absorber relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0295] [Surfactants] The photosensitive resin composition of the present invention preferably contains a surfactant. Various surfactants can be used as the surfactant, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0296] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) of the prepared photosensitive resin composition are further improved, the uniformity of the coating thickness and the liquid saving efficiency can be further improved, and the composition's ability to follow steps is increased. In other words, when forming a film using a photosensitive resin composition containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. As a result, air bubbles are less likely to be incorporated in the stepped areas, and it is possible to more favorably form a uniform film with less thickness variation.

[0297] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include compounds described in paragraphs

[0329] to

[0334] of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0298] When the photosensitive resin composition of the present invention contains a surfactant, the surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition. The photosensitive resin composition of the present invention may contain only one type of surfactant or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0299] [Other Additives] The photosensitive resin composition of the present invention may optionally contain various additives, such as metal complexes, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-flocculation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers and flame retardants), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraph

[0183] onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph

[0237] of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs

[0101] to

[0104] ,

[0107] to

[0109] of Japanese Patent Application Publication No. 2008-250074, and the contents of these documents are incorporated herein. When these additives are incorporated, it is preferable that their total content be 3% by mass or less of the solid content of the photosensitive resin composition.

[0300] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0301] [Synthesis of Polyimide Precursors for Photosensitive Resin Compositions] [Synthesis of Resin A-1] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyclyme (diethylene glycol dimethyl ether) are mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture is cooled to -10°C, and while maintaining the temperature at -10±5°C, 17.0 g of thionyl chloride is added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 90 minutes at -12±3°C, and the mixture is stirred at room temperature for 3 hours. Next, 6000 g of water is added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) is added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered again and dried under reduced pressure at 45°C for 3 days. Next, 46.6 g of the dried powder is dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine is added and stirred at room temperature for 35 minutes. After that, it is added to 3000 g of ethanol and the precipitate is filtered. The obtained precipitate is dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added and the mixture was stirred for 4 hours. After that, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was filtered off and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of resin A-1. The molecular weight of resin A-1 was measured by gel permeation chromatography (on a standard polystyrene basis). The weight-average molecular weight (Mw) was 25,000. The structure of resin A-1 is presumed to be the structure represented by the following formula A-1.

[0302] Resin A-1 (Imidification rate: 0%)

[0303] [Synthesis of Resins A-2 to A-5] Resins A-2 to A-5, represented by the following structural formulas, are synthesized in the same manner as resin A-1, or by known methods, except that the type of acid anhydride and diamine used as raw materials and the charging ratio are appropriately changed in synthesis example A-1. The weight-average molecular weight (Mw) of these resins is shown in Table 1 below.

[0304] Resin A-2 (Imidization rate: 0%)

[0305] Resin A-3 (Imidification rate: 0%)

[0306] Resin A-4 (Imidization rate: 0%)

[0307] Resin A-5 (Imidification rate: 0%)

[0308]

[0309] [Synthesis of resins for photosensitive resin compositions and upper film forming compositions] [Synthesis of resin A-6] 194.3 g of cyclohexanone is placed in a three-necked flask under a nitrogen atmosphere and heated to 80°C. 19.5 g, 23.9 g, and 6.6 g of monomers corresponding to each repeating unit of resin B-1 (described below) are added dropwise from left to right, and a solution of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, 2.17 g) dissolved in 105 g of cyclohexanone is added dropwise over 6 hours. After the dropwise addition is complete, the reaction is continued at 80°C for another 2 hours. After the reaction solution has cooled, it is added dropwise to a methanol:water mixture over 20 minutes, the precipitated powder is filtered off, and dried to obtain resin A-6 (31.6 g), which is an acid-degradable resin. The composition ratio (molar ratio) of each repeating unit, determined by NMR (nuclear magnetic resonance) spectroscopy, is 55 / 45. The weight-average molecular weight (Mw) of the resulting resin A-6 is 20,000, calculated from GPC as a standard polystyrene equivalent.

[0310] Resin A-6 [The composition ratio (molar ratio) of each repeating unit is shown in Table 2 below]

[0311] [Synthesis of resins A-7 to A-9 and resins B-1 to B-3] Other polymers are synthesized using the same procedure or known procedure. The structures of resins A-7 to A-9 and resins B-1 to B-3 are shown below.

[0312] Resin A-7 [The composition ratio (molar ratio) of each repeating unit is shown in Table 2 below]

[0313] Resin A-8 [The composition ratio (molar ratio) of each repeating unit is shown in Table 2 below]

[0314] Resin A-9 [The composition ratio (molar ratio) of each repeating unit is shown in Table 2 below]

[0315] Resin B-1 [The composition ratio (molar ratio) of each repeating unit is shown in Table 2 below]

[0316] Resin B-2 [The composition ratio (molar ratio) of each repeating unit is shown in Table 2 below]

[0317] Resin B-3

[0318]

[0319] [Synthesis of Resins A-10 to A-16] Resins A-10 to A-16, whose structural formulas and weight-average molecular weights are shown below, are synthesized in accordance with the synthesis methods of resins A-1 to A-5 described above and known conventional methods.

[0320] Resin A-10 (Mw: 28,000, Imidization rate: 0%)

[0321] Resin A-11 (Mw: 22,000, Imidization rate: 0%)

[0322] Resin A-12 (Mw: 30,000, Imidization rate: 0%)

[0323] Resin A-13 (Mw: 30,000, Imidization rate: 0%)

[0324] Resin A-14 (Mw: 30,000, Imidization rate: 0%)

[0325] Resin A-15 (Mw: 30,000, Imidization rate: 0%)

[0326] Resin A-16 (Mw: 29,000, Imidization rate: 0%)

[0327] [Synthesis of Resin A-17] Mix 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 200 g of gamma-butyrolactone. Stir at 45°C for 6 hours to produce a mixture of diesters of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, cool the reaction mixture to 0-5°C and, while maintaining the temperature at 0-5°C, add dropwise over 60 minutes a solution of 26.6 g (131 mmol) of N,N'-dicyclohexylcarbodiimide (DCC) dissolved in 25.0 g of gamma-butyrolactone. Next, a solution of 12.08 g (60.3 mmol) of 4,4'-diaminodiphenyl ether dissolved in 75 g of NMP was added dropwise over 60 minutes. After the addition was complete, the mixture was stirred at room temperature for 2 hours, then 24.2 g of ethanol was added and the mixture was stirred at room temperature for 1 hour, followed by the addition of 100 ml of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The polyimide precursor was then precipitated in 3 liters of water, and the water-polyimide precursor mixture was stirred at 600 rpm (revolutions per minute) for 30 minutes. The polyimide precursor was obtained by filtration, dissolved in 300 ml of tetrahydrofuran, and then the polyimide precursor was again precipitated in 2 liters of water. The obtained polyimide precursor was dried under reduced pressure at 45°C for 24 hours to obtain resin A-17, which is the polyimide precursor. The weight-average molecular weight of this resin A-17 is 30,000. １ The structure of resin A-17 obtained by H-NMR is presumed to contain repeating units represented by the following formula. １ H-NMR was used to confirm that the HEMA adoption rate was 100%.

[0328] Resin A-17 (Mw: 30,000, Imidization rate: 20%)

[0329] [Synthesis of Resin A-18] Resin A-18, a polyimide precursor, is obtained by the same method as in the synthesis of Resin A-17, except that 12.08 g (60.3 mmol) of 4,4'-diaminodiphenyl ether is replaced with 12.19 g (57.4 mmol) of 4,4'-diamino-2,2'-dimethylbiphenyl. The weight-average molecular weight of this Resin A-18 is 20,000.

[0330] Resin A-18 (Mw: 20,000, Imidization rate: 20%)

[0331] [Synthesis of Resin A-19] Resin A-19, a polyimide precursor, is obtained in the same manner as in the synthesis of Resin A-17, except that 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride is replaced with 12.01 g (38.7 mmol) of 4,4'-oxydiphthalic anhydride and 7.59 g (25.8 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride, and the amount of 4,4'-diaminodiphenyl ether charged is changed to 11.95 g (59.7 mmol). The weight-average molecular weight of this Resin A-19 is 28,000.

[0332] Resin A-19 (Mw: 28,000, Imidization rate: 20%)

[0333] [Synthesis of Resin A-20] Resin A-20, a polyimide precursor, is obtained in the same manner as in the synthesis of Resin A-17, except that 12.08 g (60.3 mmol) of 4,4'-diaminodiphenyl ether is replaced with 6.42 g (59.3 mmol) of 1,4-phenylenediamine. The weight-average molecular weight of this Resin A-20 is 24,000.

[0334] Resin A-20 (Mw: 24,000, Imidization rate: 20%)

[0335] [Synthesis of Resin A-21] 26.2 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 6.6 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 1.5 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) are dissolved in 49 g of N-ethylpyrrolidone (NEP) to obtain a solution. Next, 4.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 13.2 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), and 1.4 g of p-aminophenol are dissolved in 148 g of NEP, and 40 mL of cyclopentyl methyl ether (CPME) is added. While maintaining a temperature below 40°C, the above diamine solution is added dropwise to the acid anhydride solution over 1 hour, and then the reaction is carried out at 165°C for 24 hours. During the reaction, reflux and dehydration are carried out using a Dean-Stark filter. After the reaction is complete, the mixture is cooled to 25°C. To the above reaction solution, 0.90 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 26.3 g of 4-chloromethylstyrene, 28.6 g of potassium carbonate powder, 3.4 g of potassium iodide, and 66 g of NEP are added, and the mixture is carried out at 85°C for 2 hours. After the reaction is complete, the mixture is cooled to 25°C, diluted with 300 mL of NEP, solids are removed by filtration, and the mixture is further washed with 150 mL of NEP. Next, the reaction solution is added dropwise to a mixture of 2.0 liters of water and 1.0 L of methanol, stirred for 60 minutes, and then the polyimide resin is filtered. Next, the above resin is added to a mixture of 1.0 liter of tetrahydrofuran and 1.0 liter of methanol and stirred for 60 minutes. The polyimide resin is filtered and dried under reduced pressure at 40°C for 20 hours to obtain 44.7 g of polyimide resin, resin A-21. The weight-average molecular weight of resin A-21 is 28,000. １ The imidization rate of resin A-21 by H-NMR is 100%.

[0336] [Synthesis of Resins A-22 to A-27] Resins A-22 to A-27 were synthesized in the same manner as resin A-21, except that the raw materials were changed to obtain the structures shown in Table 3 below. The weight-average molecular weight and imidization rate of these resins are shown in Table 3 below.

[0337]

[0338] The structures in Table 3 are shown below. In the following formulas, * indicates the bond position.

[0339] Aa-1

[0340] Aa-2

[0341] Aa-3

[0342] Aa-4

[0343] Aa-5

[0344] Ab-1

[0345] Ab-2

[0346] Ab-3

[0347] Ab-4

[0348] Ad-1

[0349] Ad-2

[0350] Ad-3

[0351] [Preparation of Photosensitive Resin Compositions] Mix the components shown in Table 4 below to prepare photosensitive resin compositions PR-1 to PR-70. The content of each component shall be the amount (parts by mass) indicated in the "parts by mass" column of each column in Table 4 below. The obtained photosensitive resin compositions shall be subjected to pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.5 μm.

[0352]

[0353] [Preparation of Upper Film Forming Compositions] Mix the components shown in Table 5 below to prepare upper film forming compositions TC-1 to TC-8. The content of each component shall be the amount (parts by mass) indicated in the "parts by mass" column of each column in Table 5 below. The obtained upper film forming compositions shall be subjected to pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.5 μm.

[0354]

[0355] The names or structures of components other than the resins listed in Tables 4 and 5 above are shown below.

[0356] [Polymerizable Compounds] C-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) C-2: Dipentaerythritol Hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "A-DPH") C-3: NK Ester A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) C-4: Light Ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) C-5: DPGDA (manufactured by Daicel Ornex Co., Ltd.) C-6: Dicyclopentanyl Dimethacrylate (manufactured by Sartomer Co., Ltd. "SR-834NS")

[0357] [Photosensitive agent] D-1: Compound with the following structure D-2: Compound with the following structure D-3: Compound with the following structure D-4: Compound with the following structure D-5: Compound with the following structure D-6: Compound with the following structure D-7: Compound with the following structure D-8: Compound with the following structure D-9: Compound with the following structure D-10: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0358] D-7

[0359] D-8

[0360] D-8

[0361] [Antioxidant] E-1: Compound with the following structure E-2: Para-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0362] [Metal Adhesion Modifiers] F-1: Compound with the following structure F-2: Compound with the following structure F-3: Compound with the following structure F-4: Compound with the following structure

[0363] F-3

[0364] F-4

[0365] [Rust Inhibitors] G-1: Compound with the following structure G-2: Compound with the following structure G-3: Compound with the following structure G-4: Compound with the following structure

[0366] [Metal complexes] H-1: Compound with the following structure H-2: Compound with the following structure

[0367] [Thermobase Generating Agents] I-1: Compound with the following structure I-2: Compound with the following structure

[0368] [Acid diffusion control agents] K-1: Trioctylamine K-2: Tetrabutylammonium hydroxide

[0369] [Solvents] L-1: Dimethyl sulfoxide L-2: γ-Butyrolactone L-3: Propylene glycol monomethyl ether acetate (PGMEA) L-4: Propylene glycol monomethyl ether (PGME) L-5: Diisoamyl ether L-6: 4-Methyl-2-pentanol L-7: γ-Valerolactone L-8: N-Ethylpyrrolidone L-9: 3-Methoxy-N,N-dimethylpropanamide L-10: Cyclohexanone

[0370] [Examples 1-125 and Comparative Examples 1-3] A photosensitive resin composition described in Table 5 below is applied to a 300 mm diameter silicon wafer with a thin copper layer formed on its surface by spin coating, and baked (Soft Bake; SB) under the conditions described in Table 6 below to form a photosensitive resin composition layer with a thickness of 7 μm after film formation. Next, the top layer forming composition described in Table 6 below is applied to the obtained photosensitive resin composition layer by spin coating, and baked (Soft Bake; SB) at 110°C for 1 minute to form a top layer with a thickness of 300 nm after film formation. Subsequently, using a circle via mask in which a pattern with a diameter of 5 μm is arranged with a spacing of 20 μm vertically and horizontally, an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) is used to expose the entire silicon wafer at the exposure amount described in Table 5 below. Subsequently, if specified, the wafer is baked (Post Exposure Bake; PEB) under the conditions shown in Table 6 below, then developed by paddled with the developer shown in Table 6 below for 30 seconds, and if specified, rinsed by paddled with the rinse solution shown in Table 6 below, and then rotated at a rotation speed of 4000 rpm for 30 seconds. The upper layer film is removed by the above development process, and then a photosensitive resin composition layer with a circle via pattern is obtained by performing a post-bake process under the conditions shown in Table 6 below. Table 6 below also shows the SP values ​​of the solvent (upper layer solvent) and developer of the upper layer film forming composition.

[0371] [Evaluation of Dimensional Uniformity] The dimensional uniformity of the obtained circle via pattern is measured using a measuring SEM (Scanning Electron Microscope) (Hitachi: S9380II). The diameter of 1000 arbitrary via patterns is measured within an 80 mm square area, and the average value and standard deviation are calculated. The value obtained by dividing the standard deviation by the average value is calculated, and the performance is judged according to the following criteria. A smaller value obtained by dividing the standard deviation by the average value indicates that uniform patterning can be achieved over a wide range, and represents higher performance. The results are shown in Table 6 below.

[0372] -Evaluation Criteria- A: The value obtained by dividing the standard deviation by the mean is 0.03 or less. B: The value obtained by dividing the standard deviation by the mean is greater than 0.03 and 0.05 or less. C: The value obtained by dividing the standard deviation by the mean is greater than 0.05 and 0.10 or less. D: The value obtained by dividing the standard deviation by the mean is greater than 0.10.

[0373]

[0374] The types of developer and rinse solutions listed in Table 6 above are shown below. Dev-1: Cyclopentanone Dev-2: Butyl acetate Dev-3: Propylene glycol monomethyl ether acetate (PGMEA) Dev-4: 2.38% by mass aqueous solution of tetramethylammonium hydroxide Dev-5: Pure water Dev-6: Dimethyl sulfoxide:PGMEA = 1:1 mixture (volume ratio) Dev-7: 4-methyl-2-pentanol

[0375] The results shown in Tables 1 to 6 indicate that when an upper film is used in step 2 of the redistribution layer formation process, where the transmittance with respect to the exposure wavelength is not increased by exposure, a pattern with excellent dimensional uniformity cannot be obtained (Comparative Examples 1 and 2). Furthermore, when a developer that does not contain organic solvents is used in step 4 of the redistribution layer formation process, a pattern with excellent dimensional uniformity cannot be obtained (Comparative Example 3).

[0376] In contrast, when an upper layer film whose transmittance to the exposure wavelength increases with exposure is used in step 2 of the redistribution layer formation process, and a developer containing an organic solvent is used in step 4 of the redistribution layer formation process, it can be seen that a pattern with excellent dimensional uniformity can be obtained over a wide area of ​​80 mm square (Examples 1 to 125). In particular, from a comparison between Examples 2 and 18 to 21, it can be seen that when the upper layer film is a layer whose transmittance to the exposure wavelength increases by 10% or more with exposure, the dimensional uniformity of the pattern is better, and when the layer whose transmittance to the exposure wavelength increases by 20% or more with exposure, the dimensional uniformity of the pattern is even better.

[0377] Furthermore, the pattern formation method according to the present invention can be used for forming redistribution layers. For example, insulating film via patterns obtained by heating the patterns obtained in Examples 1 to 10 and Examples 18 to 22 at a heating rate of 10°C / min under a nitrogen atmosphere, and then heating at 230°C for 2 hours, can be suitably used for insulating film via pattern formation in redistribution layer formation by the semi-additive method. Also, line and space patterns obtained by performing the same pattern formation method as in Examples 11 to 17, except that the mask pattern is changed from a square via pattern to a line and space pattern, can be suitably used as a mold for the plating process in redistribution layer formation by the semi-additive method. In redistribution layer formation by the semi-additive method, both the insulating film via pattern formation and the line and space pattern formation for the plating process can be applied, or either one can be applied.

[0378] [Other Examples] In the evaluation of Examples 83 to 125, the resolution evaluation was performed in the same manner as above, except that the exposure method was changed as follows, and it was confirmed that the same results were obtained. <Exposure Method> The obtained composition layer was exposed using a direct writing exposure apparatus (SCREEN Semiconductor Solutions Co., Ltd.: DW-3100, wavelength 375 nm) by laser direct imaging.

[0379] 1. Substrate 2. Photosensitive resin composition layer 2a. Exposed area of ​​the photosensitive resin composition layer 2b. Unexposed area of ​​the photosensitive resin composition layer 3. Upper film 3a. Exposed area of ​​the upper film (area with increased transmittance) 3b. Unexposed area of ​​the upper film 4. Conductive area

Claims

1. A method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises, in this order: a step 1 for applying a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer whose dissolution rate into an organic solvent decreases upon exposure; a step 2 for forming an upper layer film on the photosensitive resin composition layer whose transmittance to the exposure wavelength increases upon exposure; a step 3 for pattern exposure of the laminate of the photosensitive resin composition layer and the upper layer film; a step 4 for removing the unexposed portion of the photosensitive resin composition layer and the upper layer film in the laminate with a developer containing the organic solvent to obtain a negative-type pattern consisting of the exposed portion of the photosensitive resin composition layer; and a step 5 for forming a conductive portion using the negative-type pattern as a template by plating.

2. The method for manufacturing a semiconductor device according to claim 1, wherein the upper film increases in transmittance by 10% or more with respect to the exposure wavelength upon exposure.

3. The method for manufacturing a semiconductor device according to claim 1, wherein the exposure wavelength of the pattern exposure is 350 to 410 nm.

4. The method for manufacturing a semiconductor device according to claim 1, wherein the exposure wavelength for the pattern exposure is 365 nm.

5. The method for manufacturing a semiconductor device according to claim 1, wherein the SP value of the developer is greater than the SP value of the solvent used to form the upper layer film.

6. The method for manufacturing a semiconductor device according to claim 1, wherein the developer contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene.

7. The method for manufacturing a semiconductor device according to claim 1, wherein the insulating portion comprises at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

8. The method for manufacturing a semiconductor device according to claim 1, wherein the photosensitive resin composition is a crosslinked negative composition.

9. The method for manufacturing a semiconductor device according to claim 1, wherein the photosensitive resin composition is a chemically amplified polarity conversion negative type composition.

10. The method for manufacturing a semiconductor device according to claim 1, wherein the pattern exposure is exposure by laser direct imaging.

11. A composition for forming an upper film used in a method for manufacturing a semiconductor device according to any one of claims 1 to 10, the composition comprising a photodecolorizable material.

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