Method for producing composite, method for producing semiconductor device, resin composition for forming insulating part, and photosensitive resin composition

Abstract

The present invention addresses the problem of providing: a method for producing a composite excellent in pattern resolution; a method for producing a semiconductor device; a resin composition for forming an insulating part; and a photosensitive resin composition. A method for producing a composite according to the present invention is a method for producing a composite comprising a substrate, an insulating part, and a conductive part, and comprises: a step for producing a laminated pattern in which a second negative resist pattern is formed on a part of a first negative resist pattern; a step for performing plating using the laminated pattern as a mold to form the conductive part; a step for removing the laminated pattern; a step for forming the insulating part on at least a part of a surface of the conductive part; and the like.

Description

Method for manufacturing a composite, method for manufacturing a semiconductor device, resin composition for forming an insulating part, and photosensitive resin composition

[0001] The present invention relates to a method for manufacturing a composite, a method for manufacturing a semiconductor device, a resin composition for forming an insulating part, and a photosensitive resin composition.

[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] In recent years, studies have been conducted on creating multilayer redistribution layers, and it is known that semi-additive processes (SAP) are used in the manufacturing of these redistribution layers (see, for example, Non-Patent Document 1).

[0004] Teck-Chong Lee, et al., “Chip Last Fanout Chip on Substrate (FOCoS) Solution for Chiplets Integration”, 2022 IEEE 72nd Electronic Components and Technology Conference (ECTC), p.1970-1974

[0005] The inventors investigated known semi-additive methods, such as those described in Non-Patent Document 1, and found that the resolution of the patterns (especially via patterns) was poor, indicating room for improvement in miniaturizing the wiring (conductive parts).

[0006] Therefore, the object of the present invention is to provide a method for manufacturing a composite with excellent pattern resolution, a method for manufacturing a semiconductor device, a resin composition for forming an insulating part, and a photosensitive resin composition.

[0007] As a result of diligent research into the above-mentioned problems, the inventors of the present invention have found that when a composite comprising a substrate, an insulating part, and a conductive part is manufactured through a predetermined processing step, the pattern resolution is excellent, and thus the present invention has been completed. In other words, the inventors of the present invention have found that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A method for manufacturing a composite comprising a substrate, an insulating portion, and a conductive portion, comprising: step 1 applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator to a substrate to form a first photosensitive resin composition layer; step 2 pattern exposing the first photosensitive resin composition layer; step 3 removing the unexposed portion of the first photosensitive resin composition layer after pattern exposure with a developer containing an organic solvent to form a first negative-type resist pattern; step 4 applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator to at least the first negative-type resist pattern to form a second photosensitive resin composition layer; step 5 pattern exposing the second photosensitive resin composition layer; step 6 removing the unexposed portion of the second photosensitive resin composition layer after pattern exposure with a developer containing an organic solvent to produce a laminated pattern in which a second negative-type resist pattern is formed on a part of the first negative-type resist pattern; A method for manufacturing a composite, comprising the steps of: 1) Plating the laminated pattern as a template to form a conductive portion (step 7); 2) Peeling off the laminated pattern (step 8); and 3) Forming an insulating portion on at least a part of the surface of the conductive portion (step 9), in this order. [2] A method for manufacturing a composite according to [1], wherein the insulating portion is formed using a resin composition B containing at least one resin (B) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. [3] A method for manufacturing a composite according to [2], wherein step 9 is a step of applying the resin composition B once. [4] A method for manufacturing a composite according to any one of [1] to [3], further comprising step 9, a step 10 of removing the insulating portion formed on the surface of the conductive portion opposite to the substrate. [5] A method for manufacturing a composite according to [4], wherein step 10 is a wet etching process. [6] A method for manufacturing a composite according to [4], wherein step 10 is a dry etching process. [7] A method for manufacturing a composite according to [4], wherein step 10 is a chemical mechanical polishing process.[8] A method for producing a composite according to any one of [1] to [7], wherein the developer used in at least one of step 3 and step 6 comprises 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. [9] A method for producing a composite according to any one of [1] to [8], wherein the exposure wavelength in step 2 and step 5 is in the range of 350 to 450 nm.

[10] A method for producing a composite according to [2], wherein the resin (B) comprises any structure represented by the following formula. In the above formula, * represents a bond position.

[11] The method for producing a composite according to [2] or

[10] , wherein the weight-average molecular weight of the resin (B) is 30,000 to 200,000.

[12] The method for producing a composite according to [2],

[10] or

[11] , wherein the resin composition B further contains a nitrogen-containing heterocyclic compound.

[13] The method for producing a composite according to any one of [2] and

[10] to

[12] , wherein the resin composition B further contains at least one antioxidant selected from the group consisting of phenol compounds, phosphite ester compounds, thioether compounds, and phosphonite compounds.

[14] The method for producing a composite according to [2], wherein the resin composition B further contains an adhesive containing an alkoxysilyl group.

[15] The method for producing a composite according to any one of [1] to

[14] , wherein the photoacid generator contained in the photosensitive resin composition used in at least one of step 1 and step 4 is a photoacid generator that generates an acid that does not contain an alkyl fluoride group.

[16] A method for producing a composite according to any one of [1] to

[15] , wherein the photoacid generator contained in the photosensitive resin composition used in at least one of step 1 and step 4 is a nonionic photoacid generator.

[17] A method for producing a semiconductor device, comprising a preparation step of preparing a semiconductor element and a redistribution layer formation step of forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step is a step of producing a composite having a substrate, an insulating portion and a conductive portion as a redistribution layer by the method for producing a composite according to any one of [1] to

[16] .

[18] An insulating portion forming resin composition used in the method for producing a composite according to any one of [1] to

[16] or the method for producing a semiconductor device according to

[17] , comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

[19] A photosensitive resin composition used in a method for producing a composite according to any one of [1] to

[16] , or a method for producing a semiconductor device according to

[17] , the photosensitive resin composition comprising a resin whose polarity changes upon the action of an acid and a photoacid generator.

[0009] According to the present invention, it is possible to provide a method for manufacturing a composite with excellent pattern resolution, a method for manufacturing a semiconductor device, a resin composition for forming an insulating part, and a photosensitive resin composition.

[0010] Figure 1A is a schematic cross-sectional view illustrating step 1 in the manufacturing method of the composite of the present invention, and is a schematic cross-sectional view showing the formation of the first photosensitive resin composition layer 2 on the substrate 1. Figure 1B is a schematic cross-sectional view illustrating step 2 in the manufacturing method of the composite of the present invention, and is a schematic cross-sectional view showing the formation of exposed areas 2a and unexposed areas 2b on the first photosensitive resin composition layer by pattern exposure from the position of the arrow. Figure 1C is a schematic cross-sectional view illustrating step 3 in the manufacturing method of the composite of the present invention, and is a schematic cross-sectional view showing the removal of the unexposed areas 2b on the first photosensitive resin composition layer by a developer containing an organic solvent, and the formation of the first negative-type resist pattern on the substrate 1. Figure 1D is a schematic cross-sectional view illustrating step 4 in the manufacturing method of the composite of the present invention, and is a schematic cross-sectional view showing the formation of the second photosensitive resin composition layer 3 on at least the first negative-type resist pattern. Figure 1E is a schematic cross-sectional view illustrating step 5 in the manufacturing method of the composite of the present invention, and is a schematic diagram of the cross-section showing how the exposed portion 3a and unexposed portion 3b of the second photosensitive resin composition layer are created by pattern exposure from the position of the arrow. Figure 1F is a schematic cross-sectional view illustrating step 6 in the manufacturing method of the composite of the present invention, and is a schematic diagram of the cross-section showing how the unexposed portion 3b of the second photosensitive resin composition layer is removed by a developer containing an organic solvent, and how a laminated pattern 4 is created in which the second negative type resist pattern is formed on a part of the first negative type resist pattern. Figure 1G is a schematic cross-sectional view illustrating step 7 in the manufacturing method of the composite of the present invention, and is a schematic diagram showing how the conductive portion 5 is formed by a plating process using the laminated pattern 4 as a template. Figure 1H is a schematic cross-sectional view illustrating step 8 in the manufacturing method of the composite of the present invention, and is a schematic diagram showing how the laminated pattern 4 is peeled off. Figure 1I is a schematic cross-sectional view illustrating step 9 in the manufacturing method of the composite of the present invention, and is a schematic diagram showing how an insulating portion 6 is formed on at least a part of the surface of the conductive portion 5. Figure 1J is a schematic cross-sectional view illustrating step 10 in the manufacturing method of the composite of the present invention, and is a schematic diagram showing the removal of the insulating portion 6 formed on the surface of the conductive portion 5 opposite to the substrate 1.

[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 composite is described as "above" or "below," it is sufficient that the other layers are 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 "above," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that this setting of upper and lower directions is for convenience in this specification, and in actual embodiments, the "above" 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 a Composite] The present invention provides a method for manufacturing a composite comprising a substrate, an insulating portion, and a conductive portion, and comprises the following steps 1 to 9 in this order. Step 1: A step of applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator onto a substrate to form a first photosensitive resin composition layer. Step 2: Pattern exposure of the first photosensitive resin composition layer. Step 3: Removing the unexposed portion of the first photosensitive resin composition layer after pattern exposure with a developer containing an organic solvent to form a first negative-type resist pattern. Step 4: Applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator to at least the first negative-type resist pattern to form a second photosensitive resin composition layer. Step 5: Pattern exposure of the second photosensitive resin composition layer. Step 6: Removing the unexposed portion of the second photosensitive resin composition layer after pattern exposure with a developer containing an organic solvent to create a laminated pattern in which the second negative-type resist pattern is formed on a part of the first negative-type resist pattern. Step 7: Plating treatment is performed using the laminated pattern as a template to form a conductive portion. Step 8: Peeling off the laminated pattern. Step 9: Forming an insulating portion on at least a part of the surface of the conductive portion.

[0013] As described above, the manufacturing method of the composite of the present invention results in good pattern resolution. The reason for this is generally presumed to be as follows: In this invention, a negative-type resist pattern is formed using a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator, and a laminated pattern formed by stacking two of these negative-type resist patterns is used as a template, which is presumed to result in good pattern resolution. The following describes in detail each step of the manufacturing method of the composite of the present invention.

[0014] [Step 1: Formation of the first photosensitive resin composition layer] Step 1 is a step of forming a first photosensitive resin composition layer by applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator onto a substrate.

[0015] Figure 1A is a schematic cross-sectional view illustrating step 1, showing the formation of the first photosensitive resin composition layer 2 on the substrate 1. In step 1, a photosensitive resin composition is applied to the substrate 1 to form the first photosensitive resin composition layer 2. In the example in Figure 1A, an example is shown in which the first photosensitive resin composition layer 2 is formed in contact with the substrate 1, but the process is not limited to this, and the first photosensitive resin composition layer 2 may be formed on the substrate 1 via other layers not shown. In the example in Figure 1A, an example is shown in which the first 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 first photosensitive resin composition layer 2 may be formed on at least a portion of one side of the substrate 1. Furthermore, the first photosensitive resin composition layer 2 may be formed on both sides of the substrate 1.

[0016] 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.

[0017] 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 10 minutes.

[0018] <Substrate> The substrate to which the photosensitive resin composition is applied is a component that supports the laminated structure of the insulating part and the conductive part (for example, a redistribution layer) described later. 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).

[0019] In this invention, semiconductor elements described later may be used as substrates. Similarly, package substrates may be used as substrates. Hereinafter, a package substrate is a substrate used when mounting semiconductor elements onto a motherboard or the like.

[0020] <First Photosensitive Resin Composition Layer> The first photosensitive resin composition layer is a layer formed using a photosensitive resin composition containing a resin whose polarity changes upon the action of an acid and a photoacid generator. Details of the photosensitive resin composition, as well as the resin whose polarity changes upon the action of an acid and the photoacid generator, will be explained later.

[0021] In the present invention, from the viewpoint of reducing environmental impact and from the viewpoint of achieving superior effects, it is preferable that the photoacid generator contained in the photosensitive resin composition used in Step 1 and Step 4 (described later) is a photoacid generator that does not contain alkyl fluoride.

[0022] Furthermore, in the present invention, from the viewpoint of achieving superior effects, it is preferable that the photoacid generator contained in the photosensitive resin composition used in at least one of step 1 and step 4, which will be described later, is a nonionic type photoacid generator.

[0023] The thickness of the first photosensitive resin composition layer is preferably 0.5 to 20 μm, and more preferably 1 to 10 μm.

[0024] [Step 2: Pattern Exposure] Step 2 is a step of pattern exposure of the first photosensitive resin composition layer. Figure 1B is a schematic cross-sectional view to explain Step 2, and is a schematic cross-sectional view showing how the exposed area 2a and unexposed area 2b of the first photosensitive resin composition layer 2 are created by pattern exposure from the position of the arrow.

[0025] One method of pattern exposure is to selectively expose the first photosensitive resin composition layer. Selective exposure means exposing only a portion of the first photosensitive resin composition layer. By selective exposure, exposed and unexposed areas are formed in the first photosensitive resin composition layer.

[0026] 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.

[0027] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0028] 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 laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser with second harmonic 532 nm and third harmonic 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 first photosensitive resin composition layer is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0029] In the present invention, from the viewpoint of achieving both resolution and pattern shape, the exposure wavelength for pattern exposure in step 2 and step 5 (described later) is preferably 350 to 450 nm, and more preferably 365 nm (i.e., i-line).

[0030] Furthermore, in the present invention, for the reasons why the effects of the present invention become apparent, it is preferable that the pattern exposure in step 2 and step 5 (described later) be different exposure patterns. Specifically, the exposure pattern in step 2 is preferably a via pattern, and more preferably a circle via pattern with a pore size of about 1 to 10 μm. The exposure pattern in step 5 (described later) is preferably a trench (line-shaped groove) pattern using a line-and-space mask, and more preferably a trench using a line-and-space mask in which space patterns and lines with a width of about 1 to 10 μm are formed in a 1:1 ratio.

[0031] <Post-exposure heat treatment> Step 2 may include a post-exposure heat treatment (post-exposure bake) in which the first 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.

[0032] [Step 3: Formation of the First Negative Resist Pattern] Step 3 is a step in which the unexposed portion of the first photosensitive resin composition layer after pattern exposure is removed with a developer containing an organic solvent to form a first negative resist pattern. Here, a negative pattern refers to a pattern in which the unexposed portion is removed and the exposed portion remains; therefore, the first negative resist pattern is a resist pattern formed in the exposed portion of the first photosensitive resin composition layer. Figure 1C is a schematic cross-sectional view for explaining Step 3, and is a schematic diagram of a cross-section showing the state in which the unexposed portion 2b of the first photosensitive resin composition layer is removed and a negative pattern consisting of the exposed portion 2a of the first photosensitive resin composition layer is formed.

[0033] 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.

[0034] In the present invention, from the viewpoint of achieving superior resolution and development uniformity, it is preferable that the developer used in step 3 and at least one of step 6, described later, 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.

[0035] 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.

[0036] The developing solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0037] <Rinsing Process> Step 3 may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after obtaining the negative type pattern. Alternatively, methods such as supplying the rinsing solution before the developer remaining on the negative type pattern dries completely may be employed.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0042] <Heat Treatment> Step 3 may include a heat treatment (post-bake) in which the obtained first negative resist 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, resins such as polyimide precursors undergo cyclization to become resins such as polyimide. Crosslinking of unreacted crosslinkable groups also proceeds.

[0043] 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.

[0044] [Step 4: Formation of the second photosensitive resin composition layer] Step 4 is a step of forming a second photosensitive resin composition layer by applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator to at least the first negative-type resist pattern. Figure 1D is a schematic cross-sectional view for explaining Step 4, and is a schematic cross-sectional view showing how the second photosensitive resin composition layer 3 is formed on at least the first negative-type resist pattern (exposed portion 2a of the first photosensitive resin composition layer). Furthermore, as shown in Figure 1D, the second photosensitive resin composition layer 3 may be formed not only on the first negative-type resist pattern (exposed portion 2a of the first photosensitive resin composition layer), but also on the substrate 1, that is, on the substrate 1 that is exposed by removing the unexposed portion 2b of the first photosensitive resin composition layer with the developer in Step 3.

[0045] As a means of applying the photosensitive resin composition onto the first negative resist pattern, coating is preferred, and specific examples thereof include the same methods as those described above for applying the photosensitive resin composition onto the substrate in step 1.

[0046] Step 4 may include a heat treatment (soft bake) in which the photosensitive resin composition applied to the first negative resist pattern is heated. This removes components such as solvents from the photosensitive resin composition applied to the first negative resist pattern. 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 10 minutes.

[0047] <Second Photosensitive Resin Composition Layer> The second photosensitive resin composition layer is a layer formed using a photosensitive resin composition containing a resin whose polarity changes upon the action of an acid and a photoacid generator. Details of the photosensitive resin composition, as well as the resin whose polarity changes upon the action of an acid and the photoacid generator, will be explained later.

[0048] The thickness of the second photosensitive resin composition layer is preferably 0.5 to 20 μm, and more preferably 1 to 10 μm.

[0049] [Step 5: Pattern Exposure] Step 5 is a step of pattern exposure of the second photosensitive resin composition layer. Figure 1E is a schematic cross-sectional view to explain Step 5, and is a schematic cross-sectional view showing how the exposed area 3a and unexposed area 3b of the second photosensitive resin composition layer 3 are created by pattern exposure from the position of the arrow.

[0050] Here, the pattern exposure method, exposure amount, exposure wavelength, exposure pattern, and post-exposure heat treatment can all be those described in step 2 above.

[0051] [Step 6: Fabrication of Laminated Pattern] Step 6 is a step in which the unexposed portion of the second photosensitive resin composition layer after pattern exposure is removed with a developer containing an organic solvent, thereby fabricating a laminated pattern in which the second negative-type resist pattern (i.e., the exposed portion of the second photosensitive resin composition layer) is formed on a part of the first negative-type resist pattern. Figure 1F is a schematic cross-sectional view illustrating Step 6, and is a schematic cross-sectional view showing how a laminated pattern 4 has been fabricated in which the unexposed portion 3b of the second photosensitive resin composition layer has been removed with a developer containing an organic solvent, and the second negative-type resist pattern (exposed portion 3a of the second photosensitive resin composition) has been formed on a part of the first negative-type resist pattern (exposed portion 2a of the first photosensitive resin composition).

[0052] Here, the removal of unexposed areas using a developer containing an organic solvent, as well as any rinsing and heating treatments, can all be those described in step 3 above.

[0053] The shape of the layered pattern is not particularly limited, but as described above, when the exposure pattern in step 2 is a via pattern and the exposure pattern in step 5 is a trench pattern, the shape will be such that the via portion (through hole) and the trench portion (line-shaped groove) overlap, as shown in Figure 1F. Here, the depth of the via portion is not particularly limited, but is preferably 1 to 10 μm, more preferably 1 to 7.5 μm, and even more preferably 1 to 5 μm. The diameter of the via portion is preferably 1 to 20 μm, more preferably 1.5 to 15 μm, and even more preferably 2 to 10 μm. The diameter (width) of the trench portion is preferably 0.5 to 10 μm, more preferably 1 to 7.5 μm, and even more preferably 1 to 5 μm. The depth of the trench portion is preferably 0.5 to 10 μm, more preferably 1 to 7.5 μm, and even more preferably 1 to 5 μm.

[0054] [Step 7: Formation of conductive part] Step 7 is a step in which a plating process is performed using the laminated pattern as a mold to form a conductive part. Figure 1G is a schematic cross-sectional view to explain step 7, and is a schematic diagram showing how the conductive part 5 is formed by a plating process using the laminated pattern 4 as a mold.

[0055] Known plating methods include electroplating and electroless plating. Below is an example of a method for forming conductive parts by plating. First, a seed layer (for example, a Ti barrier layer made of titanium) is provided in the region including the surface of recesses (for example, vias and trenches) created by the formation of the laminated pattern by a method such as sputtering. The seed layer may be formed in advance on the substrate before forming the first photosensitive resin composition layer. Next, the conductive parts are 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.

[0056] <Conductive Parts> The materials constituting the conductive parts 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.

[0057] [Step 8: Peeling off the laminated pattern] Step 8 is the step of peeling off the laminated pattern. Figure 1H is a schematic cross-sectional view to explain step 8, and is a schematic diagram showing the state after peeling off the laminated pattern 4.

[0058] Here, the method for peeling off the layered pattern is not particularly limited, and conventional known methods for peeling off resist can be appropriately employed.

[0059] [Step 9: Formation of Insulating Part] Step 9 is a step in which an insulating part is formed on at least a portion of the surface of the conductive part. Figure 1I is a schematic cross-sectional view for explaining this step 9, and is a schematic diagram showing how the insulating part 6 is formed on at least a portion of the surface of the conductive part 5. Alternatively, as shown in Figure 1I, the insulating part 6 may be formed so as to cover the surface of the conductive passage 5.

[0060] <Insulating part> In the present invention, it is preferable that the insulating part is formed using a resin composition B containing at least one resin (B) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, in order to have excellent insulating properties, chemical stability, and mechanical properties. Here, the details of resin composition B and resin (B) will be described later.

[0061] The resin (B) preferably contains one of the structures represented by the following formulas, for the reason that the film strength of the insulating portion is further improved. In the following formulas, * represents the bonding position.

[0062] The weight-average molecular weight (Mw) of resin (B) is preferably 30,000 to 200,000, more preferably 35,000 to 150,000, and even more preferably 40,000 to 100,000. Here, if the Mw of resin (B) is 30,000 or more, at least one of the following can be satisfied: delamination at the interface between the insulating part and the conductive part can be further suppressed, and the film strength of the insulating part can be further improved. Also, if the Mw of resin (B) is 200,000 or less, at least one of the following can be satisfied: the resolution of the insulating part can be better, and delamination at the interface between the insulating part and the conductive part can be further suppressed.

[0063] In the present invention, it is preferable that the resin composition B further contains a nitrogen-containing heterocyclic compound, in order to suppress delamination at the interface between the insulating portion and the conductive portion. Specific examples of nitrogen-containing heterocyclic compounds include the migration inhibitor and the rust inhibitor used as the migration inhibitor in the later description of the resin composition B.

[0064] In the present invention, it is preferable that the resin composition B further contains at least one antioxidant selected from the group consisting of phenol compounds, phosphite compounds, thioether compounds, and phosphonite compounds, in order to suppress peeling at the interface between the insulating portion and the conductive portion. Here, with regard to phenol compounds, phosphite compounds, and thioether compounds, the contents of paragraphs

[0433] to

[0443] of Japanese Patent Application Publication No. 2025-020376 can be referenced, and these contents are incorporated herein. Furthermore, with regard to phosphonite compounds, the contents of paragraphs

[0041] to

[0043] of Japanese Patent Application Publication No. 2012-255142 can be referenced, and these contents are incorporated herein.

[0065] In the present invention, it is preferable that the resin composition B further contains an adhesive containing an alkoxysilyl group, in order to suppress delamination at the interface between the insulating portion and the conductive portion. Here, examples of the adhesive containing an alkoxysilyl group include the metal adhesion modifier (preferably a silane coupling agent having an alkoxysilyl group) described in the following section on the resin composition B.

[0066] In the present invention, step 9 is preferably a step in which the resin composition B is applied in one step, but it may also be a step in which the resin composition B is applied in two or more steps.

[0067] [Step 10] The present invention's method for manufacturing a composite preferably includes a step 10 after step 9 to remove the insulating portion formed on the surface of the conductive portion opposite to the substrate (hereinafter also referred to as the "upper part of the conduction passage"), because it allows for the production of a composite with better flatness. Figure 1J is a schematic cross-sectional view illustrating step 10, and is a schematic diagram showing the state after the insulating portion 6 formed on the surface of the conductive portion 5 opposite to the substrate 1 has been removed.

[0068] In the present invention, from the viewpoint of productivity, it is preferable that step 10 is a wet etching process. Here, a wet etching process refers to an etching process using a liquid, and is a process that performs etching by chemical or physical means. Wet etching may be a single-stage etching or a multi-stage etching. If the etching consists of multiple stages, each stage of etching may be the same process or a different process. As for the wet etching, any general organic solvent can be used as long as it can remove the film on top of the guideway while leaving the film present in the gaps of the guideway.

[0069] In the present invention, from the viewpoint of high process stability, it is preferable that step 10 is a dry etching process. Here, a dry etching process refers to an etching process that does not use liquid and performs etching by chemical or physical methods. Dry etching may be a single-stage etching or a multi-stage etching. If the etching consists of multiple stages, each stage of etching may be the same process or a different process. The dry etching method is not particularly limited, but reactive ion etching (RIE) is preferred. The plasma generation mechanism in reactive ion etching is not particularly limited, but a method in which the plasma density and bias voltage can be independently controlled, such as inductively coupled plasma (ICP), conductive coupled plasma (CCP), and electron cyclotron resonance (ECR), is preferred. Any known dry etching method can be used, and various conditions are appropriately determined according to the composition and application of the insulating part. For example, etching can be performed in accordance with the International Proceedings of the Society for Optical and Photonics (Proc. of SPIE) Vol. 6924, 692420 (2008), Japanese Patent Publication No. 2009-267112, etc. Alternatively, the method described in "Chapter 4: Etching" of "Semiconductor Process Textbook, Fourth Edition, Published in 2007 by SEMI Japan" can also be used.

[0070] In the present invention, a chemical mechanical polishing (CMP) process is preferred because it yields a film with excellent flatness. Here, the CMP process refers to a process in which a surface is polished and flattened using a chemical containing an abrasive and a grinding wheel. For example, in CMP, a slurry of aluminum is used. ２ O ３ or SiO ２ A solution containing an oxidizing agent and a catalyst such as Fe can be used. Examples of oxidizing agents include S ２ O ８２－ Examples of the ions include the following.

[0071] [Method for Manufacturing Semiconductor Device] The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device comprising: a preparation step of preparing a semiconductor element; and a rewiring layer formation step of forming a rewiring layer connected to the semiconductor element and including an insulating portion and a conductive portion. In the method for manufacturing a semiconductor device of the present invention, the rewiring layer formation step is a step of producing, as a rewiring layer, a composite including a substrate, an insulating portion, and a conductive portion by the above-described method for producing a composite of the present invention.

[0072] (Preparation Step) The preparation step is a step of preparing a semiconductor element. Here, the semiconductor element may include a metal wiring layer, a terminal electrically connected to the metal wiring layer, and the like, for the purpose of being electrically connected to a rewiring layer described later.

[0073] 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).

[0074] [Redistribution Layer Formation Process] The redistribution layer formation process is a process of manufacturing a composite comprising a substrate, an insulating portion, and a conductive portion as a redistribution layer using the composite manufacturing method of the present invention described above. Here, the redistribution layer formed in the redistribution layer formation process comprises a substrate, 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.

[0075] The redistribution layer formation step may include a package substrate connection step for connecting the package substrate and the redistribution layer if the substrate is not a package substrate. Preferably, the package substrate is formed on the side of the redistribution layer opposite to the side on which the semiconductor elements are formed. A known method can be used to connect the package substrate and the redistribution layer, specifically, a method using bonding wires or solder balls. This electrically connects the package substrate and the redistribution layer.

[0076] [Resin Composition for Forming Insulating Parts] The resin composition for forming insulating parts of the present invention is a resin composition for forming insulating parts (hereinafter also referred to as "insulating film forming resin composition") used in the method for producing the composite of the present invention described above, or in the method for producing the semiconductor device of the present invention described above. Furthermore, the resin composition for forming insulating parts of the present invention is a composition (i.e., the resin composition B described above) containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Furthermore, the resin composition B may be in the form of a film or a liquid, but it is preferable to be in the form of a liquid. The components contained in resin composition B and components that may be contained will be described below.

[0077] [Resin (B)] Resin (B) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Among these, polyimide and polyimide precursor are preferred, and polyimide precursor is more preferred. Resin (B) preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If resin (B) has radical polymerizable groups, resin composition B preferably contains a photopolymerization initiator (especially a radical polymerization initiator), and more preferably contains a photopolymerization initiator (especially a radical polymerization initiator) and a polymerizable compound (especially a radical crosslinking agent). Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition B. Resin (B) may also have polarity conversion groups such as acid-degradable groups. If resin (B) has acid-degradable groups, resin composition B preferably contains a photoacid generator. For example, a chemically amplified positive-type or negative-type photosensitive film can be formed from such a resin composition B.

[0078] <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).

[0079]

[0080] 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.

[0081] 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. ｚR 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.

[0082] Also, R １１１ Examples of such groups include the following. Among these, AR-8 is preferred because it exhibits superior effects compared to the present invention. Note that the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0083]

[0084] In the formula, A represents a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ２ Preferably, the group is -, -NHCO-, or a combination thereof, and may be a single bond or a C1-C3 alkylene group substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - More preferably, the group is selected from -CH ２ -, -O-, -S-, -SO ２ -, -C (CF ３ ) ２ -, or -C(CH ３ ) ２ It is even more preferable that it is -. In the formula, * represents a bonding site with another structure.

[0085] 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.

[0086]

[0087] In formula (5), R １１２The 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 - More preferably, 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 -.

[0088] 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.

[0089] 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.

[0090] 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.

[0091]

[0092] 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 alkylene groups such as ethylene groups and propylene groups, -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 refers to 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 random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of substituents 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, particularly preferably 2 or 3, and most preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, or halogen atoms. The number of alkylene oxy groups 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 number of repeating ethylene oxy groups in these groups is as described above.

[0093] In equation (2), R １１３ If R is a hydrogen atom, １１４When 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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 further widen the exposure latitude.

[0098] Formula (2-A)

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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. More preferably, the content is 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the 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).

[0103] (Molecular Weight) 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 degree of dispersion of the molecular weight 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 degree of dispersion of the molecular weight 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, the degree of dispersion of molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight. When resin composition B contains multiple types of polyimide precursors as resin (B), 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 range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimide precursors are treated as a single resin are, respectively, within the above range.

[0104] <Polyimide> 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).

[0105]

[0106] In formula (4), R １３１ represents a divalent organic group, R １３２represents a tetravalent organic group. When it has a polymerizable group, the polymerizable group is located at R １３１ and R １３２ may be located in at least one of, or may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0107] Formula (4-1)

[0108]

[0109] In formula (4-1), R １３３ is a polymerizable group, and other groups have the same definitions as in formula (4).

[0110] Formula (4-2)

[0111] In formula (4-2), at least one of R １３４ and R １３５ is a polymerizable group; when it is not a polymerizable group, it is a monovalent organic group, and other groups have the same definitions as in formula (4).

[0112] Examples of the polymerizable group include groups containing the above-mentioned ethylenically unsaturated bond, or polymerizable groups other than groups having the above-mentioned ethylenically unsaturated bond. R １３１ represents a divalent organic group. Examples of the divalent organic group include the same ones as R １１１ in formula (2), and the preferred range is also the same. Examples of R １３１ include diamine residues remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic diamines, cycloaliphatic diamines, and aromatic diamines. Specific examples include the examples of R １１１ in formula (2) of the polyimide precursor.

[0113] R １３１ is preferably a diamine residue having at least two alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more of either or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and still more preferably, it is the above diamine and is a diamine residue not containing an aromatic ring.

[0114] 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.

[0115] R １３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５ Similar 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.

[0116] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from a tetracarboxylic dianhydride. １３２ A specific example of this is R in formula (2) of the polyimide precursor. １１５ Examples include: From the standpoint of film strength, R １３２ Preferably, the aromatic diamine residue has one to four aromatic rings.

[0117] R １３１ and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１ Preferred candidates include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0118] Polyimide is a material in which all repeating units are R １３１ and R １３２The 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.

[0119] (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 the film strength, insulating properties, etc. of the resulting film. There is no particular upper limit to the above imidization rate, and it is sufficient if it is 100% or less. The above imidization rate is measured by, for example, 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

[0120] (Molecular Weight) 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 bending resistance of the film after curing 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 resin composition B contains multiple types of polyimide as resin (B), 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, respectively, within the above range.

[0121] <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.

[0122] <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.

[0123] <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.

[0124] <Polyamideimides> Examples of polyamideimides include the compounds described in paragraphs

[0125] to

[0138] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference. Polyimide precursors, etc., are produced, for example, by the methods described in paragraphs

[0134] to

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

[0125] <Content> The content of resin (B) in resin composition B 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 resin composition B. Furthermore, the content of resin in resin composition B 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 most preferably 95% by mass or less, based on the total solid content of resin composition B. Resin composition B may contain only one type of resin (B) 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.

[0126] The resin composition B may also preferably contain at least two types of resins. Specifically, the resin composition B may contain a total of two or more types of resin (B) and other resins described later, or it may contain two or more types of resin (B), but it is preferable that it contains two or more types of resin (B). When the resin composition B contains two or more types of resin (B), for example, a polyimide precursor with a structure derived from dianhydride (R in formula (2) above) １１５ Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0127] [Other Resins] Resin composition B may contain the resin (B) described above and other resins different from resin (B) (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 resin composition B 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) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to resin composition B, the coatability of resin composition B, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0128] If resin composition B 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, even more preferably 5% by mass or more, and most preferably 10% by mass or more, relative to the total solid content of resin composition B. The content of the other resins in resin composition B 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, relative to the total solid content of resin composition B. As a preferred embodiment of resin composition B, the content of the other resins can be low. In the above embodiment, the content of the 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, relative to the total solid content of resin composition B. The lower limit of the above content is not particularly limited and may be 0% by mass or more. Resin composition B may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0129] [Metal Adhesion Modifier] From the viewpoint of improving adhesion to metal materials used in electrodes and wiring, etc., the resin composition B preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers 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.

[0130] <Silane Coupling Agents> Examples of silane coupling agents include the compounds described in paragraph

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

[0067] to

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

[0050] to

[0058] of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. In addition, R below represents a structure derived from a blocking agent in the blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and activated methylene compounds. For example, from the viewpoint of wanting the desorption temperature to be 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0131]

[0132] 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).

[0133]

[0134] 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.).

[0135] When resin composition B contains a metal adhesion improver, the content of the metal adhesion improver 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 (B). A content above the lower limit ensures good adhesion between the pattern and the conductive part, while a content below the upper limit ensures good heat resistance and mechanical properties of the pattern. Resin composition B may contain only one type of metal adhesion improver, or it may contain two or more types. If it contains two or more types, the total amount is preferably within the above range.

[0136] [Migration Inhibitor] Resin composition B preferably further contains a migration inhibitor.

[0137] 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.

[0138] As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions can also be used.

[0139] 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.

[0140] Specific examples of migration inhibitors include the following compounds.

[0141]

[0142] If resin composition B 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, relative to the total solid content of photosensitive resin composition A. Resin composition B may contain only one type of migration inhibitor or two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0143] [Polymerizable Compound] Resin composition B preferably contains a polymerizable compound. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0144] <Radical Crosslinking Agent> Resin composition B 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.

[0145] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and 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, it is preferable that it has 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition B contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0146] 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.

[0147] 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 preferred. 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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).

[0152] 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 Unexamined Patent Publication No. 62-039418. Compounds having an amino structure or a sulfide structure in 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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 more functional radical crosslinking agents include diallyl phthalate and allyl compounds such as triallyl trimellitate.

[0157] (Content) When resin composition B contains a radical crosslinking agent, 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 resin composition B. 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.

[0158] 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.

[0159] <Other Crosslinking Agents> Resin composition B 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 their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or photobase generator, and more preferably compounds having multiple groups in their 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.

[0160] (Content) If resin composition B contains other crosslinking agents, 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, relative to the total solid content of resin composition B. Resin composition B may contain only one type of other crosslinking agent, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0161] [Polymerization Initiator] The resin composition B 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, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0162] 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 －１It 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.

[0163] 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.

[0164] Examples of ketone compounds include the compounds described in paragraph

[0087] of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0165] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferred as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0166] As α-hydroxyketone 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.

[0167] As α-aminoketone 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.

[0168] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs

[0161] to

[0163] of International Publication No. 2021 / 112189 can also be suitably used. This information is incorporated herein.

[0169] Oxime compounds are preferred as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0170] As for oxime compounds, the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication 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 Publication 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 like, which are incorporated herein by reference.

[0171] As oxime compounds, for example, compounds with the following structures are preferred: 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 resin composition B, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a >C=N-O-C(=O)- linking group in its molecule.

[0172]

[0173] 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.

[0174]

[0175] 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.

[0176] 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.

[0177] <Content> When resin composition B 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, relative to the total solid content of resin composition B. Resin composition B may contain only one type of polymerization initiator or 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.

[0178] [Solvent] Resin composition B preferably contains a solvent. Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0179] 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).

[0180] 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.

[0181] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0182] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, as well as cyclic terpenes such as limonene.

[0183] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0184] 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.

[0185] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0186] 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.

[0187] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0188] 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.

[0189] <Solvent Content> From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the composition 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.

[0190] [Other Additives] Resin composition B may contain other additives. Such additives may include, for example, photoacid generators, sensitizers, chain transfer agents, base generators, metal adhesion modifiers (e.g., silane coupling agents, aluminum-based adhesion aids), migration inhibitors, polymerization inhibitors, light absorbers, surfactants, metal complexes, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers and flame retardants). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, by reference to paragraphs

[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 are incorporated herein. When these additives are incorporated, their total content is preferably 20% by mass or less of the solid content of resin composition B, more preferably 10% by mass or less, and even more preferably 3% by mass or less.

[0191] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention is a photosensitive resin composition used in the above-described method for producing the composite of the present invention or the above-described method for producing the semiconductor device of the present invention, and is a photosensitive resin composition (hereinafter also referred to as "photosensitive resin composition A" or "composition A") that contains a resin whose polarity changes due to the action of an acid (hereinafter also referred to as "resin (A)") and a photoacid generator. The components contained in photosensitive resin composition A and components that may be contained therein will be described below.

[0192] [Resin (A)] Resin (A) 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 a polar group (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 (A) 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.

[0193] <Acid-degradable groups> Acid-degradable groups are groups that decompose upon the action of an acid to produce a polar group. Acid-degradable groups preferably have 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.

[0194] 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.

[0195] Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0196] As acid-degradable groups, groups in which the hydrogen atoms of these groups are replaced with groups that are eliminated by acid are preferred. Examples of groups that are eliminated by acid (leaving groups) include -C(R ３６ ) (Caution ３７ ) (Caution ３８ ), -C(R ３６ ) (Caution ３７ ) ( OR ３９ ), and -C(R ０１ ) (Caution ０２ ) ( OR ３９ Examples include the following. In the formula, R ３６ ~R ３９ Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ and R ３７ These elements may be joined together to form a ring. ０１ and R ０２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0197] R ３６ ~R ３９ , R ０１ and R ０２ The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, and octyl group. ３６ ~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.

[0198] <Preferred Embodiments> The resin (A) preferably has repeating units represented by the following formula (A).

[0199] Formula (A)

[0200] In formula (A), 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.

[0201] The resin (A) preferably has repeating units represented by the following formula (AI) as 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.

[0202]

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212]

[0213]

[0214]

[0215] Furthermore, it is preferable that the resin (A) has repeating units having acid-degradable groups, as described in paragraphs

[0057] to

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

[0216] Furthermore, resin (A) 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.

[0217] The repeating unit having an acid-degradable group may be of one type or two or more types may be used in combination.

[0218] The content of repeating units having acid-degradable groups in resin (A) (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 (A). In particular, it is preferable that resin (A) 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 (A) is 40 mol% or more.

[0219] Resin (A) 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 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.

[0220] <Molecular Weight> The weight-average molecular weight (Mw) of resin (A) 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-forming ability 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.

[0221] <Content> The content of resin (A) 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, based on the total solid content of photosensitive resin composition A. 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 (A) may be used alone or in combination of multiple types.

[0222] [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 (A) and / or a resin other than resin (A) described above. More specifically, the photoacid generator may be linked to resin (A) and / or a resin other than resin (A) via a chemical bond. As the photoacid generator, known compounds and mixtures thereof that generate acid upon irradiation with active light or radiation, which are 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.

[0223] As mentioned above, 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. Furthermore, as mentioned above, the photoacid generator is preferably a nonionic type photoacid generator.

[0224] Furthermore, the photoacid generator preferably includes at least one compound 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.

[0225] <Oxime Sulfonate Compounds> Compounds having an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compounds") are not particularly limited as long as they have an oxime sulfonate group, but it is preferable that they be oxime sulfonate compounds represented by formulas (OS-103), (OS-104), and (OS-105).

[0226]

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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 of 6 to 30 carbon atoms, which may have substituents. １１ The substituents that the aryl group represented by may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, sulfonic acid groups, aminosulfonyl groups, and alkoxysulfonyl groups.

[0231] R １１ Preferred aryl groups represented by are phenyl group, p-methylphenyl group, trimethylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group.

[0232] 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 of 4 to 30 carbon atoms, which may have substituents. １１ The substituents that the heteroaryl group represented by may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, sulfonic acid groups, aminosulfonyl groups, and alkoxysulfonyl groups.

[0233] 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, for example, a heteroaromatic ring and a benzene ring may be fused together. １１ Examples of heteroaryl groups represented by include groups obtained by removing one hydrogen atom from a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring, which may have substituents.

[0234] In the above formulas (OS-103) to (OS-105), R １２ R 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), two or more R are present in the compound. １２ Preferably, one or two of them are alkyl groups, aryl groups, or halogen atoms; more preferably, one is an alkyl group, aryl group, or halogen atom; and particularly preferably, one is an alkyl group and the rest are hydrogen atoms. In the above formulas (OS-103) to (OS-105), R １２ The alkyl or aryl group represented by may have substituents. １２ The substituents that the alkyl or aryl group represented by may have are the above R １ Examples of substituents similar to those that the alkyl or aryl group in the above can have include.

[0235] In the above formulas (OS-103) to (OS-105), R １２ The alkyl group represented by is preferably an alkyl group having a total of 1 to 12 carbon atoms, which may have substituents, and more preferably an alkyl group having a total of 1 to 6 carbon atoms, which may have substituents. １２ The alkyl groups that are represented are preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-hexyl, allyl, chloromethyl, bromomethyl, methoxymethyl, and benzyl groups; more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and n-hexyl groups; even more preferably methyl, ethyl, n-propyl, n-butyl, and n-hexyl groups; and particularly preferably methyl.

[0236] In the above formulas (OS-103) to (OS-105), R １２ The aryl group represented by is preferably an aryl group having a total of 6 to 30 carbon atoms, which may have substituents. 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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 Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (structure shown below, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (structure shown below, manufactured by Midori Chemical Co., Ltd.), and the like.

[0245] <Idomisosulfonate Compounds> Examples of compounds having an imidosulfonate group (hereinafter also referred to as "imidosulfonate compounds") include the compound represented by the general formula (ZV).

[0246]

[0247] 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.

[0248] 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).

[0249] As the alkylene group for A, an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), as the alkenylene group for A, an alkenylene group having 2 to 12 carbon atoms (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, an arylene group having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) can be each exemplified. Among them, a naphthylene group is a preferred example when the exposure wavelength is an i-line. Specific examples of the imidosulfonate compound include, but are not limited to, the compounds described in paragraphs 0092 to 0097 of International Publication No. WO 2015 / 064602.

[0250] <Compounds Having at Least One Cation Selected from the Group Consisting of Sulfonium Cations and Iodonium Cations> A compound having at least one cation selected from the group consisting of sulfonium cations and iodonium cations is preferably a compound whose anion is non-nucleophilic and which generates an organic acid having a pKa of -1 or less upon photolysis, and more preferably a compound having a sulfonate anion, sulfonylimide anion, bis(alkylsulfonyl)imide anion, or tris(alkylsulfonyl)methyl anion as the anion. More preferably, compounds represented by the following general formula (ZI) or (ZII) can be mentioned.

[0251]

[0252] In the above general formula (ZI), R ２０１ , R ２０２ and R ２０３ each independently represent an organic group. R ２０１ , R ２０２ and R ２０３ as the organic group generally have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Further, two of R ２０１ to R ２０３ may be bonded to each other 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. R ２０１ to R ２０３Examples of the group formed by bonding two of these include an alkylene group (e.g., butylene group, pentylene group). Z － include sulfonate anions (such as aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions), carboxylate anions (such as aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions and the like.

[0253] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and preferred examples include linear or branched alkyl groups having 1 to 30 carbon atoms and cycloalkyl groups having 3 to 30 carbon atoms.

[0254] Preferred examples of the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion include aryl groups having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

[0255] 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.

[0256] 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.

[0257] An example of a sulfonyliimide anion is the saccharin anion.

[0258] 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 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.

[0259] Z － Particularly preferred is the anion represented by the following general formula (AN1).

[0260]

[0261] In the formula, Xf 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.

[0262] 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.

[0263] 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.

[0264] 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.

[0265] 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.

[0266] 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.

[0267] 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).

[0268] 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).

[0269] 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.

[0270] 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:

[0271] 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.

[0272] <Content> 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 photosensitive resin composition A. The photoacid generator may be contained alone or in combination of two or more types. When the photosensitive resin composition A contains two or more types of photoacid generators, it is preferable that their total content be within the above range.

[0273] [Other Additives] Photosensitive resin composition A 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 resins different from resin (A)), acid diffusion control agents, solvents, surfactants, onium carboxylates, and the like. For other additives, refer to paragraphs

[0204] to

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

[0274] 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.

[0275] [Synthesis of Resin (A)] [Synthesis of Resin A-1] 194.3 g of cyclohexanone is placed in a three-necked flask under a nitrogen atmosphere and heated to 80°C. A solution prepared by dissolving three monomers corresponding to each repeating unit of resin A-1 represented by the following formula (19.5 g, 23.9 g, and 6.6 g from left to right) and polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 3.17 g) 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 the acid-degradable resin resin A-1 (31.6 g) shown below. The composition ratio (molar ratio) of the repeating units determined by NMR (nuclear magnetic resonance) is 40 / 50 / 10. The weight-average molecular weight of the resulting resin A-1 is 20,000, calculated from GPC as standard polystyrene equivalent.

[0276] Resin A-1 [The composition ratio (molar ratio) of each repeating unit is shown in Table 1 below]

[0277] [Synthesis of resins A-2 to A-5] Resins A-2 to A-5, represented by the following structural formulas, are synthesized using the same method as resin A-1, or by known methods.

[0278] Resin A-2 [The composition ratio (molar ratio) of each repeating unit is shown in Table 1 below]

[0279] Resin A-3 [The composition ratio (molar ratio) of each repeating unit is shown in Table 1 below]

[0280] Resin A-4 [The composition ratio (molar ratio) of each repeating unit is shown in Table 1 below]

[0281] Resin A-5 [The composition ratio (molar ratio) of each repeating unit is shown in Table 1 below]

[0282] [Synthesis of Resin (B)] [Synthesis of Resin B-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 diglyme (diethylene glycol dimethyl ether) are mixed, and the mixture is stirred at a temperature of 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture is cooled to -10°C, and 17.0 g of thionyl chloride is added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution prepared by dissolving 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture at -12±3°C over 90 minutes, and the mixture is stirred at room temperature for 3 hours. Then, 6000 g of water is added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. After stirring, the precipitate (solid polyimide precursor) is collected by filtration 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. After stirring, the precipitate (solid polyimide precursor) is filtered again and dried under reduced pressure at 45°C for 3 days. Then, after 46.6 g of the dried powder is dissolved in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine is added, and the mixture is stirred at room temperature for 35 minutes. Thereafter, the mixture is added to 3000 g of ethanol, and the precipitate is collected by filtration. The obtained precipitate is dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) are added thereto, and the mixture is stirred for 4 hours. Thereafter, the ion exchange resin is removed by filtration, and the obtained polymer solution is added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate is collected by filtration and dried under reduced pressure at 45°C for 24 hours, whereby 45.1 g of Resin B-1 is obtained. The molecular weight of Resin B-1 is measured by gel permeation chromatography (in terms of standard polystyrene). The weight average molecular weight (Mw) is 25,000. The structure of Resin B-1 is estimated to be the structure represented by the following formula B-1.

[0283] Resin B-1

[0284] [Synthesis of Resins B-2 to B-7] Resins B-2 to B-7, represented by the following structural formulas, are synthesized in the same manner as resin B-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 B-1. The weight-average molecular weight (Mw) of these resins is shown in Table 2 below.

[0285] Resin B-2

[0286] Resin B-3

[0287] Resin B-4

[0288] Resin B-5

[0289] Resin B-6

[0290] Resin B-7

[0291] [Preparation of Photosensitive Resin Compositions] Mix the components shown in Table 3 below to prepare photosensitive resin compositions PR-1 to PR-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 3 below. The obtained photosensitive resin compositions shall be subjected to pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.5 μm.

[0292]

[0293] [Preparation of Insulating Resin Compositions] Mix the components shown in Table 4 below to prepare insulating resin compositions PI-1 to PI-11. 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 insulating resin compositions shall be subjected to pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.5 μm.

[0294]

[0295] The names or structures of components other than the resins listed in Tables 3 and 4 above are shown below.

[0296] [Photosensitive agent] C-1: Compound with the following structure C-2: Compound with the following structure C-3: Compound with the following structure C-4: Compound with the following structure

[0297] [Acid diffusion control agents] D-1: Trioctylamine D-2: Tetrabutylammonium hydroxide

[0298] [Crosslinking agent] E-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0299] [Antioxidant] F-1:4-Methoxyphenol

[0300] [Metal Adhesion Modifier] G-1: Compound with the following structure

[0301] [Rust Inhibitor] H-1: Compound with the following structure H-2: Compound with the following structure

[0302] [Metal Complexes] I-1: Compounds with the following structure

[0303] [Thermobase Generating Agents] J-1: Compound with the following structure J-2: Compound with the following structure

[0304] [Thermal polymerization initiator] K-1: Compound with the following structure

[0305] [Solvents] L-1: Propylene glycol monomethyl ether acetate (PGMEA) L-2: Propylene glycol monomethyl ether (PGME) L-3: Dimethyl sulfoxide L-4: γ-Butyrolactone

[0306] [Examples 1-8: Fabrication of Laminated Copper Wiring] The insulating film formation resin composition PI-4 is applied to a silicon wafer by spin coating and dried at 110°C for 5 minutes. The temperature is then increased at a rate of 10°C / min under a nitrogen atmosphere and heated to 230°C for 2 hours. This forms a polyimide insulating film with a thickness of 8 μm. Next, a Ti barrier layer with a thickness of 50 nm and a Cu seed layer with a thickness of 150 nm are formed on the obtained polyimide insulating film in that order by sputtering to obtain a laminate. Next, the composition used to form the first negative resist pattern described in Table 5 below is applied to the obtained laminate by spin coating and baked at 110°C for 3 minutes (Soft Bake; SB) to form a first photosensitive resin composition layer with a thickness of 5 μm after film formation. Subsequently, using a mask with a 3 μm circle via pattern arranged at 3 μm intervals vertically and horizontally, an i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) was used to measure 200 mJ / cm². ２ Exposure is performed with the specified exposure dose. After that, the wafer is baked at 110°C for 3 minutes (Post Exposure Bake; PEB), then developed by paddled with the developer shown in Table 5 below for 30 seconds, and the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds. After that, a via pattern as the first negative resist pattern is obtained by baking at 150°C for 3 minutes (Post Bake; PB). Next, the composition used to form the second negative resist pattern described in Table 5 below is applied to the obtained via pattern by spin coating, and baked at 110°C for 3 minutes (Soft Bake; SB) to form a second photosensitive resin composition layer with a film thickness of 5 μm after film formation. Subsequently, a line-and-space mask was used to form a 2.4 μm space pattern with a line-to-space ratio of 1:1. An i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) was used to measure 200 mJ / cm². ２Exposure is performed with the specified exposure dose. Then, after baking at 110°C for 3 minutes (Post Exposure Bake; PEB), the wafer is developed by paddled for 30 seconds with the developer shown in Table 5 below, and the wafer is rotated at 4000 rpm for 30 seconds. Afterward, a layered pattern is obtained by baking at 150°C for 3 minutes (Post Bake; PB), forming a line and space pattern as a second negative resist pattern on the via pattern. Next, the obtained layered pattern is subjected to sulfuric acid treatment (contact with a 10% by mass sulfuric acid aqueous solution for 60 seconds), followed by rinsing with water. Finally, the substrate with the layered pattern is immersed in 300 mL of copper plating solution (product name "CU8502", manufactured by Dow Ch Emical), with a plating bath temperature of 25°C and a current density of 2 A / dm². ２ The wafer is set to a specific temperature and electroplated for 10 minutes to form plated copper throughout the entire interior of the via pattern and up to a height of 2.5 μm in the space portion of the line-and-space pattern. Next, the composite film consisting of the laminated pattern (template) and plated copper is immersed in a resist stripping solution (JELK-001, manufactured by Kanto Chemical Co., Ltd.) at 60°C for 5 minutes, and then rinsed with pure water to strip the laminated pattern. Furthermore, the Cu seed layer and Ti barrier layer are wet-etched by sequentially treating them with Cu seed etching solution and Ti seed etching solution, and the processed wafer is observed using a cross-sectional SEM (Hitachi: S4800). It is confirmed whether a laminated copper wiring has been formed, in which the second layer of line-shaped copper pattern is connected and stacked on top of the first layer of via-shaped copper pattern.

[0307] [Comparative Example 1: Fabrication of Multilayer Copper Wiring by Semi-Additive Method] The insulating film-forming resin composition PI-11 is applied to a silicon wafer by spin coating and dried at 110°C for 5 minutes. The resulting insulating film-forming resin composition layer is subjected to a 400 mJ / cm² injection using an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) with a mask in which 3 μm circle via patterns are arranged at 3 μm intervals vertically and horizontally. ２Exposure is performed with the specified exposure dose. Next, the material is developed with cyclopentanone until the unexposed areas are removed, rinsed with PGMEA for 30 seconds, and then heated in a nitrogen atmosphere at a heating rate of 10°C / min to 230°C for 2 hours. This forms a first insulating film with a thickness of 3 μm and patterned with 3 μm circle vias. Next, a Ti barrier layer with a thickness of 50 nm and a Cu seed layer with a thickness of 150 nm are formed on the obtained first insulating film in that order by sputtering. Then, the photosensitive resin composition PR-8 is applied by spin coating and baked at 110°C for 3 minutes (Soft Bake; SB) to form a photosensitive resin composition layer with a thickness of 3 μm. Subsequently, a line-and-space mask was used to form a 2.4 μm space pattern with a line-to-space ratio of 1:1. An i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) was used to measure 400 mJ / cm². ２ Exposure treatment is performed with the specified exposure dose. Then, the wafer is developed by paddled with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 30 seconds, followed by rinsing with pure water, and then the wafer is rotated at 4000 rpm for 30 seconds. This results in a laminated pattern in which a line-and-space pattern made of a photosensitive resin composition is formed on an insulating film on which a via pattern is formed. Next, the obtained laminated pattern is subjected to sulfuric acid treatment (contact with a 10% by mass sulfuric acid aqueous solution for 60 seconds) and then rinsed with water. Afterward, the substrate with the laminated pattern is immersed in 300 mL of copper plating solution (product name "CU8502", manufactured by Dow Chemical), with a plating bath temperature of 25°C and a current density of 2 A / dm². ２The wafer is set to a specific temperature and electroplated for 10 minutes to form plated copper in all areas inside the via pattern formed on the first insulating film, and up to a height of 2.5 μm in the space portion of the line-and-space pattern made of a photosensitive resin composition. Next, the wafer is immersed in a resist stripping solution (JELK-001, manufactured by Kanto Chemical Co., Ltd.) at 60°C for 5 minutes, and then rinsed with pure water to strip the laminated pattern. Furthermore, the Cu seed layer and Ti barrier layer are wet-etched by sequentially treating with Cu seed etching solution and Ti seed etching solution, and the processed wafer is observed using a cross-sectional SEM (manufactured by Hitachi: S4800). It is confirmed whether a laminated copper wiring is formed, in which line-shaped copper patterns are connected and stacked on via-shaped copper patterns.

[0308] [Examples 1-8 and Comparative Example 1: Evaluation of Circle Via Pattern Resolution] Circle via patterns are formed in the same manner as the above-described laminated copper wiring formation method, except that the dimensions of the circle via masks are changed to three types: 2.0, 2.5, and 3.0 μm. The resulting circle via patterns are observed using a cross-sectional SEM (Hitachi S4800). The smallest via mask dimension in which no residue due to poor development occurs at the via bottom and via sidewalls is measured and judged according to the following evaluation criteria. The smaller the minimum mask dimension, the better the resolution. The evaluation results for Examples 1-8 and Comparative Example 1 are shown in Table 5 below. <Evaluation Criteria> A: The smallest via mask dimension is 2.0 μm. B: The smallest via mask dimension is 2.5 μm. C: The smallest via mask dimension is 3.0 μm.

[0309] [Examples 1-8 and Comparative Example 1: Evaluation of Line and Space Pattern Resolution] A line and space pattern is formed on a via pattern using the same method as the above-described laminated copper wiring formation method, except that the space pattern dimensions of the mask for forming the line and space pattern are changed to three types: 0.8, 1.6, and 2.4 μm. The resulting line and space pattern is observed using a cross-sectional SEM (Hitachi S4800). The smallest space mask dimension in which the line pattern is not collapsed and no bridge residue is generated in the space area is measured and judged according to the evaluation criteria below. The smaller the minimum mask dimension, the better the resolution. The evaluation results for Examples 1-8 and Comparative Example 1 are shown in Table 5 below. <Evaluation Criteria> A: The smallest space mask dimension is 0.8 μm. B: The smallest space mask dimension is 1.6 μm. C: The smallest space mask dimension is 2.4 μm.

[0310]

[0311] The types of developer listed in Table 5 above are shown below. <Developer> Dev-1: Propylene glycol monomethyl ether acetate (PGMEA) Dev-2: Butyl acetate

[0312] The results shown in Tables 1 to 5 indicate that the multilayer copper wiring produced by the composite manufacturing method of the present invention can be obtained with high resolution. In contrast, the multilayer copper wiring produced by the semi-additive method does not have good resolution (Comparative Example 1).

[0313] [Examples 9-18: Thermal Cycle Reliability Test of Metal Wiring and Insulating Film Composites] On a silicon wafer on which multilayer copper wiring obtained by the method of Example 3 is formed, the insulating film forming resin composition described in Table 6 below is applied by spin coating and dried at 110°C for 5 minutes. Then, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated to 230°C for 2 hours. This yields a composite of multilayer copper wiring and a polyimide insulating film, in which a polyimide insulating film is formed in the space of the multilayer copper wiring and on top. The obtained composite is subjected to 500 thermal cycles from -40°C to 125°C under conditions of 85% RH humidity, according to the method specified in JIS C 60068-2-14. After that, the obtained composite film is cut perpendicular to the line and space and the cut surface is observed over a length of 100 μm using a cross-sectional SEM (Hitachi: S4800). Crack occurrence in the insulating film is judged according to the following criteria. A lower number of cracks indicates higher reliability of the composite. These results are shown in Table 6 below. <Evaluation Criteria> A: Fewer than 5 cracks in the insulating film B: 5 or more cracks in the insulating film

[0314]

[0315] The results shown in Table 6 indicate that a composite of conductive and insulating parts (redistribution layer) with excellent reliability in thermal cycling tests can be obtained.

[0316] [Example 19: Planarization of insulating film by wet etching] On a silicon wafer on which a multilayer copper wiring obtained by the method of Example 3 is formed, the insulating film forming resin composition PI-4 is applied by spin coating and dried at 110°C for 5 minutes. Next, it is immersed in a mixed solvent of cyclopentanone:PGMEA = 60:40 and wet etched until the insulating film formed on the upper part of the multilayer copper wiring is removed. Then, it is heated at 230°C for 2 hours. This yields a composite of multilayer copper wiring and a polyimide insulating film, in which a polyimide insulating film is formed in the spaces (around the conductive parts) of the multilayer copper wiring.

[0317] [Example 20: Planarization of insulating film by dry etching] On a silicon wafer on which the multilayer copper wiring obtained by the method of Example 3 is formed, the insulating resin composition PI-4 is applied by spin coating and dried at 110°C for 5 minutes. Furthermore, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 2 hours. This yields a composite film of multilayer copper wiring and a polyimide insulating film, in which a polyimide insulating film is formed in the spaces of the multilayer copper wiring and on top. Next, using a parallel plate type reactive ion etching apparatus DES-245R manufactured by Plasma Systems, the insulating film is dry etched under the following etching conditions until the polyimide insulating film formed on top of the multilayer copper wiring is removed. This yields a composite film of multilayer copper wiring and a polyimide insulating film, in which a polyimide insulating film is formed in the spaces of the multilayer copper wiring. <Etching conditions> Etching gas: O ２ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0318] [Example 21: Planarization of insulating film by CMP] On a wafer on which the multilayer copper wiring obtained by the method of Example 3 is formed, the insulating resin composition PI-4 is applied by spin coating and dried at 110°C for 5 minutes. Further heating is performed in a nitrogen atmosphere at a heating rate of 10°C / min and heated at 230°C for 2 hours. This yields a composite film of multilayer copper wiring and a polyimide insulating film, in which a polyimide insulating film is formed in the spaces of the multilayer copper wiring and on top. Next, using a CMP apparatus manufactured by Fujikoshi Machinery Industries, Ltd., CMP treatment is performed with a slurry liquid containing alumina abrasive particles until the insulating film formed on top of the multilayer copper wiring is removed. This yields a composite of multilayer copper wiring and a polyimide insulating film, in which a polyimide insulating film is formed in the spaces of the multilayer copper wiring.

[0319] [Plativity Evaluation of Examples 19-21] The flatness of the composites of multilayer copper wiring and polyimide insulating film obtained by the methods of Examples 19-21 was measured using an AFM (Atomic Force Microscope). The difference in height between the point with the maximum height and the point with the minimum height was used as an indicator of flatness and was evaluated according to the following criteria. The smaller the difference in height, the better the flatness and the better the performance in terms of being able to stack wiring layers. The results are shown in Table 7 below. <Evaluation Criteria> A: Height difference is 200 nm or less B: Height difference is greater than 200 nm and 500 nm or less C: Height difference is greater than 500 nm and 1000 nm or less D: Height difference is 1000 nm or more

[0320]

[0321] The results shown in Table 7 indicate that a composite film of metal wiring and insulating film with excellent flatness can be obtained by using the composite manufacturing method of the present invention (Examples 19-21).

[0322] 1. Substrate 2. First photosensitive resin composition layer 2a. Exposed area of ​​the first photosensitive resin composition layer 2b. Unexposed area of ​​the first photosensitive resin composition layer 3. Second photosensitive resin composition layer 3a. Exposed area of ​​the second photosensitive resin composition layer 3b. Unexposed area of ​​the second photosensitive resin composition layer 4. Lamination pattern 5. Conductive area 6. Insulating area

Claims

1. A method for manufacturing a composite comprising a substrate, an insulating portion, and a conductive portion, comprising: step 1 applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator to a substrate to form a first photosensitive resin composition layer; step 2 pattern exposing the first photosensitive resin composition layer; step 3 removing the unexposed portion of the first photosensitive resin composition layer after pattern exposure with a developer containing an organic solvent to form a first negative-type resist pattern; step 4 applying a photosensitive resin composition containing a resin whose polarity changes due to the action of an acid and a photoacid generator to at least the first negative-type resist pattern to form a second photosensitive resin composition layer; step 5 pattern exposing the second photosensitive resin composition layer; and step 6 removing the unexposed portion of the second photosensitive resin composition layer after pattern exposure with a developer containing an organic solvent to produce a laminated pattern in which a second negative-type resist pattern is formed on a part of the first negative-type resist pattern. A method for manufacturing a composite, comprising the steps of: 7) applying a plating treatment to the laminated pattern as a mold to form a conductive portion; 8) peeling off the laminated pattern; and 9) forming an insulating portion on at least a part of the surface of the conductive portion, in this order.

2. The method for producing the composite according to claim 1, wherein the insulating portion is formed using a resin composition B containing at least one resin (B) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

3. The method for producing a composite according to claim 2, wherein step 9 is a step of applying the resin composition B once.

4. A method for manufacturing a composite according to claim 1, further comprising step 9, step 10 of removing an insulating portion formed on the surface of the conductive portion opposite to the substrate.

5. The method for producing a composite according to claim 4, wherein step 10 is a wet etching process.

6. The method for producing a composite according to claim 4, wherein step 10 is a dry etching process.

7. The method for producing a composite according to claim 4, wherein step 10 is a chemical mechanical polishing process.

8. The method for producing a composite according to claim 1, wherein the developer used in at least one of step 3 and step 6 comprises 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.

9. The method for producing a composite according to claim 1, wherein the exposure wavelength in step 2 and step 5 is in the range of 350 to 450 nm.

10. The method for producing the composite according to claim 2, wherein the resin (B) includes any structure represented by the following formula. In the above formula, * represents the bonding position.

11. The method for producing the composite according to claim 2, wherein the weight-average molecular weight of the resin (B) is 30,000 to 200,000.

12. The method for producing the composite according to claim 2, wherein the resin composition B further contains a nitrogen-containing heterocyclic compound.

13. The method for producing the composite according to claim 2, wherein the resin composition B further contains at least one antioxidant selected from the group consisting of phenol compounds, phosphite compounds, thioether compounds, and phosphonite compounds.

14. The method for producing the composite according to claim 2, wherein the resin composition B further contains an adhesive containing an alkoxysilyl group.

15. The method for producing a composite according to claim 1, wherein the photoacid generator contained in the photosensitive resin composition used in at least one of step 1 and step 4 is a photoacid generator that generates an acid that does not contain an alkyl fluoride group.

16. The method for producing a composite according to claim 1, wherein the photoacid generator contained in the photosensitive resin composition used in at least one of step 1 and step 4 is a nonionic photoacid generator.

17. 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 is a step of manufacturing a composite having a substrate, an insulating portion and a conductive portion as a redistribution layer by the composite manufacturing method described in any one of claims 1 to 16.

18. A resin composition for forming an insulating portion, used in a method for producing a composite according to any one of claims 1 to 16, or a method for producing a semiconductor device according to claim 17, the resin composition comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

19. A photosensitive resin composition used in a method for producing a composite according to any one of claims 1 to 16, or in a method for producing a semiconductor device according to claim 17, the photosensitive resin composition comprising a resin whose polarity changes upon the action of an acid and a photoacid generator.

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