Method for manufacturing bonded body, bonded body, method for manufacturing laminate, method for manufacturing device, device, and composition for forming polyimide-containing precursor portion

Abstract

To provide a method for manufacturing a bonded body which can obtain a bonded body with a large maximum peeling resistance between two substrates when bonding the two substrates, a resulting bonded body, a method for manufacturing a laminate, a resulting laminate, a method for manufacturing a device and a resulting device, and a composition for forming a polyimide-containing precursor portion.SOLUTION: A method for manufacturing a bonded body includes a step of preparing a substrate A, a polyimide-containing precursor portion forming step of forming a polyimide-containing precursor portion on the surface of the substrate A that includes a wiring terminal, a step of preparing a substrate B, and a bonding step of bonding the surface of the substrate A having the polyimide-containing precursor portion and the surface of the substrate B having the wiring terminal, and the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion is 5% or more.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a method for producing a bonded body, a method for producing a laminate, a laminate, a method for producing a device, a device, and a composition for forming a polyimide-containing precursor portion. [Background technology]

[0002] Electronic devices such as mobile phones and tablet devices are becoming increasingly smaller, while their functions are becoming more diverse. To meet these needs, the electronic circuits built into these devices must be further miniaturized, highly integrated, and packaged at high density. Packaging technologies such as SIP (System in Package), MCM (Multi-Chip Module), and POP (Package on Package) are attracting attention as technologies that achieve miniaturization while maintaining multifunctionality, high performance, and reliability. These technologies are expected to reduce the number of components and simplify the semiconductor manufacturing process, thereby lowering the cost of electronic devices. By further applying the flip-chip mounting technology, techniques and materials relating to three-dimensional mounting using TSV (Through silicon via) are being studied (Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Using Permanent and Temporary Polyimide Adhesives in 3D-TSV Processing to Avoid Thin Wafer Handling (Journal of Microelectronics and Electronic Packaging (2010) 7, pp.214-219 Summary of the Invention [Problem to be solved by the invention]

[0004] In SIPs, chips are connected via wire bonding, making it difficult to achieve the same processing speed as conventional SOCs (System on Chip). Furthermore, wire bonding connections complicate the manufacturing process, leaving a need for improvements in product cost and quality. To address these challenges, the chip-on-chip (COC) packaging technology was developed. COCs connect chips via flip-chip connections, shortening transmission distances and achieving high-speed performance equivalent to SOCs. Figure 1 shows a cross-sectional view of a typical COC structure. In this example, the COC comprises a daughter chip (first substrate) 1 and a mother chip (second substrate) 2. The mother chip 2 has electronic circuits (not shown) and flip-chip electrodes (not shown). The daughter chip 1 is supported and connected to the mother chip 2 via solder electrodes (bumps) 93. The solder electrodes 93 are surrounded by underfill 94 to ensure insulation. The mother chip 2 is mounted on a base substrate 98 via a bonding film 91, maintaining insulation. The mother chip 2 and base substrate 98 are electrically connected via wire bonding pads 97b, wire bonding 96, and substrate electrodes 97a. Such a COC structure is sealed with sealing resin 95 to form a semiconductor device 90. Solder balls 99 are provided on this semiconductor device 90, and it is incorporated into an electronic device via these.

[0005] In a COC structure element as shown in Figure 1, after daughter chip 1 and mother chip 2 are connected and fixed with solder bumps 93, underfill 94 is filled into the gap between them. Therefore, a fluid resin is used as the material that makes up the underfill, and after filling between the solder bumps, it is hardened and formed. Here, daughter chip 1 and mother chip 2 are bonded together by the adhesive force of the resin, but from the perspective of improving adhesion, it is necessary to improve the maximum peel resistance between these two substrates.

[0006] Therefore, an object of the present invention is to provide a method for producing a bonded body that can produce a bonded body having a large maximum peel resistance between two substrates when bonding two substrates, and the resulting bonded body; a method for producing a laminate and the resulting laminate; a method for producing a device and the resulting device; and a composition for forming a polyimide-containing precursor portion. [Means for solving the problem]

[0007] Examples of specific embodiments of the present invention are given below. <1> A step of preparing a substrate A having a surface provided with wiring terminals; a polyimide-containing precursor part forming step of forming a polyimide-containing precursor part on the surface of the substrate A that includes the wiring terminal; preparing a substrate B having a surface provided with wiring terminals; a bonding step of bonding a surface of the substrate A having the polyimide-containing precursor portion to a surface of the substrate B having the wiring terminal, The difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more. A method for manufacturing a bonded body. <2> the cyclization rate of the polyimide in the polyimide-containing precursor part before the bonding step is 40 to 90%; <1> A method for producing the bonded body according to claim 1. <3> a cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 91 to 100%. <1> or <2> A method for producing the bonded body according to claim 1. <4> The bonding temperature in the bonding step is 380°C or less. <1> ~ <3> 10. A method for producing the bonded body according to any one of the above items. <5> the bonding temperature in the bonding step is equal to or higher than the melting point of the wiring terminal of the substrate A and equal to or higher than the melting point of the wiring terminal of the substrate B; <1> ~ <4> 10. A method for producing the bonded body according to any one of the above items. <6> The polyimide-containing precursor portion forming step includes applying a polyimide-containing precursor portion forming composition to a surface of the substrate A that includes the wiring terminals, and heating the applied polyimide-containing precursor portion forming composition at a temperature lower than the melting point of the wiring terminals of the substrate A, wherein the heating temperature is lower than the melting point of the wiring terminals. <1> ~ <5> 10. A method for producing the bonded body according to any one of the above items. <7> The substrate A is in the form of a wafer. <1> ~ <6> 10. A method for producing the bonded body according to any one of the above items. <8> The substrate B is in the form of a chip. <1> ~ <7> 10. A method for producing the bonded body according to any one of the above items. <9> The substrate B is in the form of a wafer. <1> ~ <7> 10. A method for producing the bonded body according to any one of the above items. <10> The method further includes a planarizing step of planarizing the surface of the polyimide-containing precursor portion of the substrate A, and includes the polyimide precursor portion forming step, the planarizing step, and the bonding step in this order. <1> ~ <9> 10. A method for producing the bonded body according to any one of the above items. <11> In the bonding step, the electrodes included in the surface of the substrate A having the polyimide-containing precursor portion and the electrodes on the surface of the substrate B having the wiring terminals are bonded so as to be in direct contact with each other. <1> ~ <10> 10. A method for producing the bonded body according to any one of the above items. <12> The method further includes a second polyimide-containing precursor part forming step of forming a second polyimide-containing precursor part on the surface of the substrate B that includes the wiring terminal, and includes the second polyimide-containing precursor part forming step and the bonding step in this order. <1> ~ <11> 10. A method for producing the bonded body according to any one of the above items. <13> a difference between a cyclization rate of the polyimide in the second polyimide-containing precursor portion before the bonding step and a cyclization rate of the polyimide contained in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; <12> A method for producing the bonded body according to claim 1. <14> the cyclization rate of the polyimide in the second polyimide-containing precursor part before the bonding step is 40 to 90%; <12> or <13> A method for producing the bonded body according to claim 1. <15> the substrate B has an inorganic insulating film between the wiring terminals of the substrate B; <1> ~ <11> 10. A method for producing the bonded body according to any one of the above items. <16> the polyimide-containing precursor part forming step is a step of applying a polyimide-containing precursor part forming composition onto the surface of the substrate A that includes the wiring terminal, and the polyimide-containing precursor part forming composition contains a polyimide precursor and a solvent; <1> ~ <15> 10. A method for producing the bonded body according to any one of the above items. <17> The polyimide-containing precursor portion-forming composition contains a migration inhibitor. <16> A method for producing the bonded body according to claim 1. <18> The polyimide-containing precursor portion-forming composition further contains a polymerizable compound having a ring structure. <16> or <17> A method for producing the bonded body according to claim 1. <19> The polyimide-containing precursor portion-forming composition contains a polymerizable compound whose homopolymer has a glass transition temperature of 200°C or higher. <16> ~ <18> 10. A method for producing the bonded body according to any one of the above items. <20> The polyimide-containing precursor portion-forming composition contains a filler. <16> ~ <19> 10. A method for producing the bonded body according to any one of the above items. <21> <1> ~ <20> A bonded body obtained by the manufacturing method described in any one of the above. <22> A step of preparing a substrate C having two or more surfaces provided with wiring terminals; A step of preparing a plurality of substrates D each having a surface provided with wiring terminals; a polyimide-containing precursor portion forming step of forming a polyimide-containing precursor portion on a surface of at least one of the substrates C and D, the surface including the wiring terminal; and a joining step of joining a surface of the substrate D having the wiring terminals to each of at least two of the surfaces of the substrate C having the wiring terminals, each of the plurality of bonding portions in the bonding step includes the polyimide-containing precursor portion; In at least one bonded portion, the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonded portion after the bonding step is 5% or more. A method for manufacturing a laminate. <23> the polyimide-containing precursor portion contains a filler; <22> A method for producing the laminate described in . <24> <22> or <23> A laminate obtained by the method for producing a laminate described in 1. <25> <1> ~ <20> or a method for producing a bonded body according to any one of <22> or <23> A method for manufacturing a device, comprising the method for manufacturing a laminate according to claim 1. <26> <21> or the conjugate according to <24> A device comprising the laminate described in claim 1. <27> A step of preparing a substrate A having a surface provided with wiring terminals; a polyimide-containing precursor part forming step of forming a polyimide-containing precursor part on the surface of the substrate A that includes the wiring terminal; preparing a substrate B having a surface provided with wiring terminals; a joining step of joining a surface of the substrate A having a polyimide-containing precursor part and a surface of the substrate B having the wiring terminal, the polyimide-containing precursor part is a member formed from the polyimide-containing precursor part-forming composition, The difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more. A composition for forming a polyimide-containing precursor portion. <28> the cyclization rate of the polyimide in the polyimide-containing precursor part before the bonding step is 40 to 90%; <27> The polyimide-containing precursor part forming composition according to claim 1. <29> a cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 91 to 100%. <27> or <28> The polyimide-containing precursor part forming composition according to claim 1. <30> Further comprising a filler, <27> ~ <29> 1. The polyimide-containing precursor part-forming composition according to claim 1 . [Effects of the Invention]

[0008] According to the present invention, there are provided a method for producing a bonded body that provides a bonded body with a large maximum peel resistance between two substrates when the two substrates are bonded together, and the resulting bonded body; a method for producing a laminate, and the resulting laminate; a method for producing a device, and the resulting device; and a composition for forming a polyimide-containing precursor portion. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view schematically showing the structure of a COC semiconductor device. [Figure 2] FIG. 1 is a process explanatory diagram showing, in schematic cross-sectional views, a process for bonding substrates in a method for producing a bonded body in which the polyimide-containing precursor portion-forming composition of the present invention according to one embodiment of the present invention is used. [Figure 3] 1A to 1C are process explanatory diagrams showing, in schematic cross-sectional views, the steps of bonding substrates in a method for manufacturing a bonded body using the polyimide-containing precursor portion-forming composition of the present invention according to one embodiment of the present invention (continuation of FIG. 2). [Figure 4] 1A to 1C are process explanatory diagrams showing, in schematic cross-sectional views, the steps of bonding substrates in a method for manufacturing a bonded body using the polyimide-containing precursor portion-forming composition of the present invention according to one embodiment of the present invention (continuation of FIG. 3). [Figure 5] FIG. 1 is a cross-sectional view schematically showing an example of a three-dimensionally mounted semiconductor device using TSVs. [Figure 6] FIG. 2 is a schematic cross-sectional view showing details of a substrate used in the examples. [Figure 7] FIG. 1 is a schematic cross-sectional view showing the details of the operations carried out in Examples 22 and 23. [Figure 8] FIG. 1 is a schematic cross-sectional view showing the details of the operations carried out in Examples 22 and 23. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components of the present invention may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, light used for exposure generally includes actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. In this specification, the solid content refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. Unless otherwise specified, the solid content concentration refers to the concentration at 25°C. In the present invention, the temperature is 25°C unless otherwise specified. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values ​​measured by gel permeation chromatography (GPC). In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 (manufactured by Tosoh Corporation) and a guard column such as HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, measurements are performed using THF (tetrahydrofuran) as the eluent. Furthermore, unless otherwise specified, detection is performed using a UV (ultraviolet) light detector at a wavelength of 254 nm.

[0011] (Method of manufacturing a bonded body) The method for producing a bonded body of the present invention includes the steps of: preparing a substrate A having a surface provided with wiring terminals; forming a polyimide-containing precursor portion on the surface of the substrate A having the wiring terminals; preparing a substrate B having a surface provided with wiring terminals; and bonding the surface of the substrate A having the polyimide-containing precursor portion with the surface of the substrate B having the wiring terminals, wherein the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more.

[0012] By using the method for manufacturing a bonded body of the present invention, it is possible to manufacture a bonded body having a large maximum peel resistance between two substrates, such as wafers and wafers or a wafer and a chip, when bonding two substrates via a polyimide-containing portion. Specifically, by making the difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step 5% or more, an anchor effect is obtained when the polyimide-containing precursor portion changes into the polyimide-containing portion during bonding (the cyclization rate increases), making it possible to increase the maximum peel resistance during bonding. The method for producing the bonded body of the present invention will be described in detail below.

[0013] <Step of preparing substrate A> The method for producing a bonded body of the present invention includes a step of preparing a substrate A having a surface provided with wiring terminals. In the step of preparing the substrate A, the substrate A may be manufactured by a known method (for example, plating a substrate such as a silicon substrate) or may be obtained by purchasing or other means.

[0014] [Substrate A] The substrate A has a surface having wiring terminals. Hereinafter, the wiring terminal on the substrate A will also be referred to as wiring terminal A.

[0015] The substrate A may be in the form of a wafer or a chip, but a wafer is also one of the preferred embodiments of the present invention. In the present invention, the term "wafer" refers to a substrate including a semiconductor, and is a concept that includes a panel formed of a plurality of semiconductor elements. In the present invention, a chip refers to an individual piece containing a semiconductor formed by dicing or the like, and may be a single-sided chip or a double-sided chip.

[0016] The shape of the substrate A is not particularly limited, but examples thereof include a polygonal flat plate, a disk, and a polyhedron. The thickness of the substrate A is preferably 0.1 to 5 mm, more preferably 0.2 to 1 mm. The wiring terminals A on the substrate A are preferably pillar electrodes. Furthermore, the wiring terminal A preferably contains a metal, more preferably at least one metal selected from the group consisting of tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), palladium (Pd), platinum (Pt), cobalt (Co), nickel (Ni), zinc (Zn), ruthenium (Ru), iridium (Ir), rhodium (Rh), lead (Pb), bismuth (Bi), and indium (In), and even more preferably at least one metal selected from the group consisting of copper, tin, and nickel. In this specification, the inclusion of at least one of metal X or an alloy containing such metal is collectively referred to simply as "containing metal X." Note that the alloy may contain elements other than those listed above. For example, a copper alloy may contain silicon atoms to form a Corson alloy. Furthermore, unavoidable dissolved oxygen and organic residues of raw material compounds mixed in during precipitation may be present. The wiring terminal A may be a wiring terminal including a plurality of different members. For example, the substrate may have a portion (hereinafter also referred to as "electrode") used as an electrode made of a metal such as copper, silver, gold, or an alloy containing one or more of these, and a portion (hereinafter also referred to as "conductive path") used as solder made of a metal such as nickel, tin, lead, or an alloy containing one or more of these may be formed on the copper electrode, and the electrode and the conductive path may exist in series to form one wiring terminal A. Among these, the wiring terminal A is preferably a wiring terminal A containing at least a member containing copper and a member containing tin. An example of a substrate A having a surface provided with such wiring terminal A is substrate b) used in the examples of the present application. In substrate b), a conductive path made of tin is formed on an electrode made of copper.

[0017] The material used for the electrodes is not particularly limited, and examples thereof include tin, gold, silver, copper, aluminum, tungsten, palladium, platinum, cobalt, nickel, zinc, ruthenium, iridium, rhodium, and alloys thereof. Among these, metals containing copper, metals containing aluminum, metals containing tungsten, metals containing nickel, and metals containing gold are preferred for the electrodes, metals containing copper are more preferred, and copper is even more preferred. The metal used for the electrodes is preferably a metal that does not melt even during the bonding process. The melting point of the metal used for the electrodes is preferably 500°C or higher, more preferably 700°C or higher, and even more preferably 800°C or higher. There is no particular upper limit, but it is preferably 3000°C or lower, for example. The material used for the conductive path is not particularly limited, but examples include tin, lead, silver, copper, zinc, bismuth, indium, or alloys thereof. Among these, in the present invention, solder made of tin or a tin alloy (metal containing tin) is preferred. Recently, lead-free solder technology has advanced, and it is also preferable to select such a material. The metal used for the conductive paths is preferably a metal that melts during the joining process. The melting point of the metal used for the conductive paths is preferably 400°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower. The lower limit of the melting point is not particularly limited as long as it is solid at room temperature, but is preferably 150°C or higher, for example. It is also preferable that a plurality of wiring terminals A are formed on the substrate A.

[0018] The material used for the substrate A is not particularly limited, and may include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe; paper; SOG (Spin-On-Glass); TFT (Thin Film Transistor) array substrates; and electrode plates for plasma display panels (PDPs). The substrate may have a surface layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer. In the present invention, a semiconductor substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred. The substrate A may have an electronic circuit region including an electronic circuit. The electronic circuit may include elements such as semiconductors. The electronic circuit is preferably electrically connected to the wiring terminal A. When substrate A is a wafer, the size can be 100 mm or more in diameter (maximum diameter if substrate A is not circular). For large substrates, for example, 200 mm or more is preferable, and 250 mm or more is more preferable. There is no particular upper limit, but 2,000 mm or less is preferable. When substrate A is a chip, the size is preferably 7 mm or more in diameter (maximum diameter if substrate A is not circular), more preferably 10 mm or more, and even more preferably 20 mm or more. The upper limit is, for example, preferably 50 mm or less, more preferably 40 mm or less, and even more preferably 30 mm or less.

[0019] <Polyimide-containing precursor portion forming step> The method for producing a bonded body of the present invention includes a polyimide-containing precursor part forming step of forming a polyimide-containing precursor part on the surface of the substrate A on which the wiring terminal (wiring terminal A) is provided. The polyimide-containing precursor portion is preferably formed so as to be in contact with the wiring terminals A, and more preferably so as to fill the recesses between the wiring terminals A. Furthermore, the polyimide-containing precursor portion may be formed on at least a portion of the wiring terminal A, but an embodiment in which it is formed on the entire wiring terminal A is also one of the preferred embodiments of the present invention. The polyimide-containing precursor part forming step preferably includes applying and heating a polyimide-containing precursor part forming composition onto the surface of the substrate A that includes the wiring terminals. Details of the application and heating will be described later.

[0020] [Polyimide-containing precursor portion] The polyimide-containing precursor portion is preferably a member containing a polyimide precursor, and may further contain components other than the polyimide precursor. Examples of components other than the polyimide precursor include components other than the polyimide precursor contained in the polyimide-containing precursor portion-forming composition described below, and components that are modified (decomposed, polymerized, structurally changed, etc.) by heating. The polyimide-containing precursor part preferably further contains a polymerizable compound having a ring structure. Moreover, it is preferable that the polyimide-containing precursor portion further contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher. These polymerizable compounds will be described in detail later.

[0021] The thickness of the polyimide-containing precursor portion is not particularly limited, but from the viewpoint of exerting the effects of its physical properties, the thickness immediately before the bonding step (if a planarization step described below is performed, the thickness immediately before the planarization step) is preferably 100 nm or more, more preferably 300 nm or more, even more preferably 500 nm or more, even more preferably 1 μm or more, and even more preferably 2 μm or more. There is no particular upper limit, but it is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The thickness of the film can be measured using a known film thickness measuring device.

[0022] [Applicable process] The polyimide-containing precursor portion forming process is preferably a process including applying a polyimide-containing precursor portion forming composition (hereinafter also simply referred to as a "resin composition") to the surface of the substrate A having the wiring terminal A (application process). Here, the polyimide-containing precursor portion forming step is a step of applying a polyimide-containing precursor portion forming composition to the surface of the substrate A that has the wiring terminals, and it is also preferable that the polyimide-containing precursor portion forming composition contains a polyimide precursor and a solvent. The polyimide-containing precursor part-forming composition preferably further contains a migration inhibitor. The polyimide-containing precursor portion-forming composition preferably further contains a polymerizable compound having a ring structure. The polyimide-containing precursor portion-forming composition preferably further contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher. The polyimide-containing precursor portion-forming composition, including the migration inhibitor and polymerizable compound, will be described in detail below.

[0023] Examples of methods for applying the resin composition to the substrate A 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 the film thickness, spin coating, slit coating, spray coating, and inkjet coating are more preferred, and from the viewpoint of uniformity of the film thickness and productivity, spin coating and slit coating are preferred. A film of the desired thickness can be obtained by adjusting the solid content concentration of the resin composition and coating conditions depending on the method. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. Spin coating can be applied, for example, at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes. Alternatively, a coating film formed by applying the coating to a temporary support in advance using the above application method may be transferred onto the substrate. Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention. Additionally, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing. Furthermore, a pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0024] Furthermore, when the resin composition contains a solvent, after applying the resin composition to the substrate A, a step (drying step) of drying the member made of the resin composition (hereinafter also simply referred to as "film") may be included. The drying temperature in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0025] The thickness immediately after application (thickness after drying if a drying step is performed) is not particularly limited, and may be appropriately adjusted so that the thickness of the resulting polyimide-containing precursor portion becomes the thickness described below.

[0026] The polyimide-containing precursor part forming step may include a step of patterning a member made of a resin composition. When a resin composition containing a photosensitive compound such as a photopolymerization initiator described below is used, the patterning can be performed by exposure and development. After the polyimide-containing precursor portion is formed, its surface may be planarized. Details of planarization will be described later. Note that if patterning is performed, the thickness of the portion removed by development or the like will not be used in calculating the film thickness difference (T1-T2) described later.

[0027] [Exposure process] The film may be subjected to an exposure step to selectively expose the film to light. That is, the method for producing a bonded body of the present invention may include an exposure step of selectively exposing the polyimide-containing precursor portion formed in the polyimide-containing precursor portion formation step. Selective exposure means that only a portion of the polyimide-containing precursor part is exposed, and selective exposure results in the formation of exposed and unexposed regions in the polyimide-containing precursor part. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention. For example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 is preferred, and 200 to 8,000 mJ / cm 2 is more preferred.

[0028] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0029] Examples of exposure wavelengths, in relation to the light source, include: (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps (g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer lasers (KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays (EUV) (wavelength 13.6 nm), (6) electron beams, and (7) YAG lasers (second harmonic 532 nm, third harmonic 355 nm). In the method for producing a bonded body of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and i-line exposure is particularly preferred. This allows for particularly high exposure sensitivity to be achieved. The exposure method is not particularly limited as long as it exposes at least a part of the polyimide-containing precursor portion, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0030] <Post-exposure baking process> The polyimide-containing precursor part may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a bonded body of the present invention may include a post-exposure heating step of heating the polyimide-containing precursor part exposed in the exposure step. The post-exposure baking step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. The temperature rise rate in the post-exposure heating step from the heating start temperature to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may be changed during heating as needed. The heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used. It is also preferable that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0031] <Developing process> The polyimide-containing precursor portion after exposure may be subjected to a development step in which the polyimide-containing precursor portion is developed with a developer to form a pattern. That is, the method for producing a bonded structure of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. By performing development, one of the exposed and unexposed portions of the film is removed, thereby forming a pattern. Here, development in which the non-exposed portion of the polyimide-containing precursor portion is removed by the development step is called negative development, and development in which the exposed portion of the polyimide-containing precursor portion is removed by the development step is called positive development.

[0032] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0033] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. When TMAH is used, for example, the content of the basic compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass %, based on the total mass of the developer.

[0034] When the developer contains an organic solvent, the organic solvent may be an ester, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid), ethyl, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (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 (for example, 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, etc., and acetoacetate. Examples of ethers include diethylene 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the solvent include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0035] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

[0036] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of 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, and may be 100% by mass.

[0037] The developer may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0038] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred. Alternatively, a process may be employed in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate, and this process may be repeated multiple times. As a method for supplying the developer in the development step, a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a step in which these are combined can be used.

[0039] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0040] In the development step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a rinse liquid may be supplied before the developer in contact with the pattern is completely dried.

[0041] [Rinse solution] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0042] When the rinse solution contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate), methyl ethoxyacetate, ... ethyl methyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, methyl, 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, etc., and ethoxylated methyl 2-methylpropionate. Examples of ethers include diethylene 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the solvent include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0043] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0044] When the rinse solution contains an organic solvent, the rinse solution preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Alternatively, the rinse solution may contain 100% by mass of the organic solvent.

[0045] The rinse solution may further contain other ingredients. Examples of other components include known surfactants and known defoaming agents.

[0046] [Method of supplying rinse liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle. As a method for supplying the rinse liquid in the rinsing step, a step in which the rinse liquid is continuously supplied to the substrate, a step in which the rinse liquid is kept substantially stationary on the substrate, a step in which the rinse liquid is vibrated on the substrate by ultrasonic waves or the like, or a step in which any of these is combined can be used.

[0047] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0048] <Heating process> The polyimide-containing precursor part obtained in the polyimide-containing precursor part forming step is preferably subjected to a heating step in which the polyimide-containing precursor part is heated. That is, the method for producing a bonded body of the present invention may include a heating step of heating the polyimide-containing precursor part. In the heating step, a part of the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 250°C or lower, more preferably 220°C or lower, even more preferably 200°C or lower, and can be 180°C or lower. The lower limit of the heating temperature is preferably 160°C or higher, and more preferably 170°C or higher. The cyclization rate of the polyimide in the polyimide-containing precursor portion can be adjusted by adjusting the heating conditions in the heating step, such as the heating temperature and heating time. Specifically, heating at a higher temperature for a longer period of time increases the cyclization rate of the polyimide, but the difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step decreases.

[0049] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base generated from the base generator due to heating.

[0050] In the heating step, heating is preferably carried out at a temperature increase rate of 1 to 12°C / min from the initial temperature to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. Additionally, in the case of a rapid heating oven, the temperature is preferably increased from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0051] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0052] The heating time (heating time at the maximum heating temperature) is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes.

[0053] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 200°C at a rate of 2°C / min, and held at 200°C for 10 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C. / min.

[0054] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0055] <Post-exposure process> The polyimide-containing precursor part obtained in the polyimide-containing precursor part forming step may be subjected to a post-exposure step of exposing the polyimide-containing precursor part instead of or in addition to the heating step. That is, the method for producing a bonded body of the present invention may include a post-exposure step of exposing the polyimide-containing precursor part to light. The method for producing a bonded body of the present invention may include both a heating step and a post-exposure step, or may include only one of the heating step and the post-exposure step. In the post-exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure to light of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure to light of a photoacid generator can be promoted. In the post-exposure step, it is sufficient that at least a portion of the polyimide-containing precursor portion is exposed, but it is preferable that the entire polyimide-containing precursor portion is exposed. The exposure dose in the post-exposure step is 50 to 20,000 mJ / cm, calculated as exposure energy at a wavelength to which the photosensitive compound is sensitive. 2 It is preferable that the concentration is 100 to 15,000 mJ / cm 2 It is more preferable that: The post-exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0056] <Formation of two or more layers> In one preferred embodiment of the present invention, in the polyimide-containing precursor part forming step, the polyimide-containing precursor part is formed in two or more layers. That is, the polyimide-containing precursor part may have a structure in which multiple layers made of a resin composition are laminated, but the interface between these layers may not be clear because, for example, part of the first layer dissolves in a solvent during the formation of the second layer. By configuring the polyimide-containing precursor part to have two or more layers, the flatness of the surface of the polyimide-containing precursor part is improved, which has the advantage of facilitating the flattening step described below. In the above embodiment, the polyimide-containing precursor part is preferably formed of 2 to 4 layers, more preferably 2 or 3 layers, and even more preferably 2 layers. When the polyimide-containing precursor portion is formed in two or more layers, for example, an application step (and, if necessary, a drying step) may be performed consecutively, followed by the above-mentioned exposure step, post-exposure heating step, and development step as necessary, and then the above-mentioned heating step may be performed. Alternatively, after the above-mentioned application step and, if necessary, the exposure step, post-exposure baking step, and development step are performed, the above-mentioned heating step may be performed to form a first layer, and then the above-mentioned application step and, if necessary, the exposure step, post-exposure baking step, and development step may be performed on the first layer, and then the above-mentioned heating step may be performed to form a second or subsequent layer. Furthermore, when carrying out the application step to the heating step for the first layer, the conditions for the exposure step, heating step, etc., which are carried out as necessary, may be adjusted to semi-cure the first layer, and then the application step to the heating step for the second layer and thereafter may be carried out. Furthermore, when the polyimide-containing precursor part is formed of two or more layers, the components contained in the resin compositions used to form the respective layers and the content ratios of the respective components may be the same or different.

[0057] <Step of preparing substrate B> The method for producing a bonded body of the present invention includes a step of preparing a substrate B having a surface provided with wiring terminals.

[0058] The form of the substrate B may be a wafer or a chip, which may be selected depending on the desired design of the bonded body.

[0059] [Substrate B] The substrate B has wiring terminals. Hereinafter, the wiring terminal on the substrate B will also be referred to as wiring terminal B.

[0060] The thickness of the substrate B is preferably 0.1 to 5 mm, more preferably 0.2 to 1 mm. In the bonded body obtained by the bonding step described below, it is preferable that at least a part of the wiring terminal B is electrically bonded to the wiring terminal A of the substrate A described above.

[0061] The material used for the substrate B is not particularly limited, and the same materials as those for the substrate A described above are preferably used. Moreover, the preferred embodiment of the wiring terminal B is the same as the preferred embodiment of the wiring terminal A. The substrate B may have an electronic circuit region including an electronic circuit. The electronic circuit may have an element such as a semiconductor. The electronic circuit is preferably electrically connected to the wiring terminal. When substrate B is a wafer, the diameter (maximum diameter if substrate B is not circular) can be 100 mm or more. For large substrates, for example, the diameter is preferably 200 mm or more, and more preferably 250 mm or more. There is no particular upper limit, but it is preferably 2,000 mm or less. When substrate B is a chip, the size is preferably 7 mm or more in diameter (maximum diameter when substrate B is not circular), more preferably 8 mm or more, and even more preferably 10 mm or more. The upper limit is, for example, preferably 50 mm or less, more preferably 30 mm or less, and even more preferably 20 mm or less.

[0062] Furthermore, it is also preferable that the substrate B has an inorganic insulating film between the wiring terminals. Examples of inorganic insulating films include, but are not limited to, silicon oxide films, silicon nitride films, silicon oxynitride films (the oxygen and nitrogen content ratio is not particularly limited), aluminum oxide films, aluminum nitride films, hafnium oxide films, yttrium oxide films, zirconium oxide films, gallium oxide films, tantalum oxide films, magnesium oxide films, lanthanum oxide films, cerium oxide films, neodymium oxide films, and silicon carbon nitride (SiCN) films. Specific examples of the substrate B having an inorganic insulating film include substrate c) in the examples described below. The inorganic insulating film preferably insulates the plurality of electrodes included in the wiring terminal B. Furthermore, when the substrate B has an inorganic insulating film, the second polyimide-containing precursor part forming step described below may be carried out, but an embodiment in which the second polyimide-containing precursor part forming step is not carried out is also possible.

[0063] <Second Polyimide-Containing Precursor Portion Forming Step> The method for producing a bonded body of the present invention preferably further includes, before the bonding step, a second polyimide-containing precursor part formation step of forming a second polyimide-containing precursor part on the surface of the substrate B that has the wiring terminals. The second polyimide-containing precursor part forming step can be carried out, for example, by the same method as the polyimide-containing precursor part forming step for the substrate A described above. Here, in the second polyimide-containing precursor part-forming step, the polyimide-containing precursor part-forming composition of the present invention may be used, or other known polyimide-containing precursor part-forming compositions may be used, but it is preferable to use the polyimide-containing precursor part-forming composition of the present invention. However, when the polyimide-containing precursor portion-forming composition of the present invention is used in the second polyimide-containing precursor portion-forming step, the composition of the polyimide-containing precursor portion-forming composition of the present invention used in the second polyimide-containing precursor portion-forming step and the composition of the polyimide-containing precursor portion-forming composition used in the polyimide-containing precursor portion-forming step for substrate A may be the same as or different from each other. A preferred embodiment of the second polyimide-containing precursor part is the same as the preferred embodiment of the polyimide-containing precursor part formed on the substrate A described above. In the bonding step described below, it is believed that the adhesion of the bonded body is improved by bonding the second polyimide-containing precursor part and the polyimide-containing precursor part formed on the above-mentioned substrate A so that they are in contact with each other at least in part.

[0064] [Flattening process] The method for producing a bonded body of the present invention preferably includes a planarizing step of planarizing the surface of the polyimide-containing precursor portion of the substrate A between the polyimide-containing precursor portion forming step and the bonding step. In the bonding step described below, the planarized polyimide-containing precursor portion of the substrate A is preferably bonded so as to come into contact with the surface of the substrate B (or the surface of the second polyimide-containing precursor portion, which may also be planarized).

[0065] By the planarization, the wiring terminals A on the substrate A are preferably exposed from the polyimide-containing precursor portion. Furthermore, in the substrate A and the polyimide-containing precursor portion after the planarization, the wiring terminal A and the polyimide-containing precursor portion may be at the same height, or the wiring terminal A may be recessed relative to the polyimide-containing precursor portion, or the polyimide-containing precursor portion may be recessed relative to the wiring terminal A. Here, the difference in height between the wiring terminal A and the polyimide-containing precursor portion is preferably ±1 μm or less, and more preferably ±0.5 μm or less. The planarization may be performed by physical polishing such as cutting, mechanical polishing, grinding, plasma treatment, or laser ablation, or by chemical polishing such as CMP (Chemical Mechanical Polishing). The polishing rate of the polyimide-containing precursor portion during the planarization is preferably 200 nm / min or more, more preferably 400 nm / min or more, even more preferably 900 nm / min or more, and even more preferably 1800 nm / min or more. The upper limit of the polishing rate is not particularly limited, but is preferably less than 3000 nm / min from the viewpoint of controlling the in-plane uniformity of the polished object. The polishing rate of the wiring terminals A on the substrate A during the planarization is preferably equal to or less than the polishing rate of the polyimide-containing precursor portion, and more preferably equal to or less than half the polishing rate of the polyimide-containing precursor portion. The slurry used for the CMP is not particularly limited, but silica slurry, ceria slurry, alumina slurry, etc. can be used. The particle size of the slurry is not particularly limited, but from the viewpoint of scratch prevention, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 200 nm or less. The lower limit of the particle size of the slurry is not particularly limited, but from the viewpoint of polishing rate, it is preferably 10 nm or more. Furthermore, these methods may be combined, such as by performing CMP after cutting. Specifically, for example, the surface of the polyimide-containing precursor part is cut with a diamond cutting tool to expose a new surface of the polyimide-containing precursor part and the wiring terminal A. By performing a planarization process on the wiring terminal A and the polyimide-containing precursor part on the substrate A so that the wiring terminal A is exposed, it becomes possible to expose the top of the wiring terminal A by planarizing the wiring terminal A and the polyimide-containing precursor part all at once. The planarization can be performed using, for example, a surface planer. Examples of surface planers include those with a diamond bit attached to a spindle, such as DFS8910, DFS8960, DAS8920, and DAS8930 (all trade names) manufactured by Disco Corporation.

[0066] -TTV- In the planarization step, the polyimide-containing precursor portion is preferably planarized together with the wiring terminal A. As for the degree of planarization, the TTV (Total Thickness Variation) of the polyimide-containing precursor portion and the wiring terminal A is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. In the present invention, TTV refers to the arithmetic mean value of the thickness differences (T1-T2) of the remaining compartments, obtained by dividing the area at least 1 mm inward from the edge of the polyimide-containing precursor into 2 mm square compartments (if the area of ​​the polyimide-containing precursor is too small to be divided into 2 mm square compartments, the entire area at least 1 mm inward from the edge of the polyimide-containing precursor is considered as one compartment), measuring the maximum thickness (T1) between one surface and the other surface for each compartment, and calculating the thickness difference (T1-T2) for each compartment. The compartments are ranked in descending order of thickness difference (T1-T2), and excluding a number of compartments equivalent to 10% (rounded down if there is a decimal point) of the total number of compartments in descending order of thickness difference, starting from the top compartment (with the largest thickness difference) and a number of compartments equivalent to 10% (rounded down if there is a decimal point) of the total number of compartments in descending order of thickness difference, starting from the bottom compartment (with the smallest thickness difference). In this specification, when specifically referring to the TTV of the polyimide-containing precursor portion defined herein, it may be referred to as "compartment evaluation TTV." By setting the TTV of the polyimide-containing precursor portion to the above upper limit or less, the film thickness becomes generally uniform and the adhesion to the substrate B is improved.

[0067] -Ra- The polyimide-containing precursor part of the present invention preferably has a surface roughness Ra of 10 nm or more and 1.5 μm or less on the surface opposite to the side in contact with the surface of the substrate A. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, even more preferably 300 nm or less, still more preferably 200 nm or less, even more preferably 150 nm or less, and still more preferably 120 nm or less. By making the surface roughness of the polyimide-containing precursor portion equal to or greater than the lower limit, an anchor effect is exerted, and the adhesiveness to the substrate B can be improved. Furthermore, by setting the surface roughness to the above upper limit or less, it is possible to effectively prevent defects such as voids from occurring when bonding with the substrate B due to bubbles or the like being included in the bonding.

[0068] When forming the second polyimide-containing precursor part on the substrate B, it is preferable to include a second planarization step of planarizing the surface of the second polyimide-containing precursor part between the second polyimide-containing precursor part formation step and the bonding step. The second planarization step can be carried out by the same method as the planarization step for substrate A described above.

[0069] <Joining process> The method for producing a bonded body of the present invention includes a bonding step of bonding the surface of the substrate A having the polyimide-containing precursor portion and the surface of the substrate B having the wiring terminal. When the substrate B has a second polyimide-containing precursor portion, the bonding step is a step of bonding the surface of the substrate A having the polyimide-containing precursor portion to the surface of the substrate B having the second polyimide-containing precursor portion.

[0070] By bonding, wiring terminal A on substrate A and wiring terminal B on substrate B are electrically bonded. In one preferred embodiment of the present invention, in the bonding step, an electrode included in the surface of the substrate A having the polyimide-containing precursor portion and an electrode on the surface of the substrate B having the wiring terminal are bonded so as to be in direct contact with each other. That is, it is also preferable that neither the wiring terminal A nor the wiring terminal B has a conductive path.

[0071] The bonding is preferably carried out by a means including heating, and more preferably by a means including heating and pressure. The temperature during bonding (bonding temperature) is preferably 100° C. or higher, more preferably 150° C. or higher, and even more preferably 180° C. or higher. The upper limit is preferably 450° C. or lower, more preferably 400° C. or lower, even more preferably 380° C. or lower, particularly preferably 350° C. or lower, even more preferably 300° C. or lower, even more preferably 280° C. or lower, even more preferably 260° C. or lower, and even more preferably 250° C. or lower. As described above, this temperature is preferably a temperature near the melting point of the conductive paths, in consideration of melting the conductive paths and enabling bonding between the electrodes. The heating time in the bonding step is not particularly limited, but is preferably 5 seconds or more, more preferably 1 minute or more, and even more preferably 2 minutes or more. The practical upper limit is 30 minutes or less. The heating environment is not particularly limited, but it is preferable to perform the heating in a reduced pressure atmosphere while mechanically pressurizing the polyimide-containing precursor part. -5 Preferably, the pressure is 1×10 mbar or more. -4 More preferably, 5×10 mbar or more -4 The upper limit is preferably 0.1 mbar or less, and more preferably 1×10 -2 More preferably, it is 5×10 mbar or less. -3 It is even more preferred that it is below mbar. The bonding is preferably performed by sandwiching two substrates (substrate A and substrate B), and it is preferable to apply pressure to the substrates at this time. The pressure applied to the substrates is preferably 1 kN or more, more preferably 5 kN or more, and even more preferably 10 kN or more. A practical upper limit is 100 kN or less. There are no particular restrictions on the equipment used in the bonding step, but equipment used for reflow soldering of electronic components can be suitably used.

[0072] In addition, in the bonding step, it is also preferable that the temperature of the substrate A having the polyimide-containing precursor portion is preheated to 70° C. or higher. In addition, when the substrate B contains the second polyimide-containing precursor portion, it is also preferable that the temperature of the substrate B is preheated to 70° C. or higher. The temperature is preferably 70° C. or higher, and more preferably 90° C. or higher. The upper limit of the temperature is not particularly limited, but is preferably 130° C. or lower. According to the above aspect, the tact time of the joining process can be reduced. Furthermore, the fluidity of the polyimide-containing precursor portion during bonding may be improved, resulting in an increase in the maximum peel resistance.

[0073] The joining step converts the polyimide-containing precursor portion into a polyimide-containing portion. Here, when the substrate B has a second polyimide-containing precursor portion, the polyimide-containing portion is formed from the polyimide-containing precursor portion and the second polyimide-containing precursor portion.

[0074] The thermal diffusivity of the polyimide-containing part is 2.0×10 -7 m 2 s -1 It is preferable that the value is 3.0×10 or more. -7 m 2 s -1 More preferably, it is 5.0×10 or more. -7 m 2 s -1 More preferably, it is equal to or greater than this. The thermal diffusivity of the polyimide-containing portion can be adjusted, for example, by designing the type of filler material when the polyimide-containing portion contains a filler, the particle size of the filler (when two or more types of fillers are contained, the combination of particle sizes), the thermal diffusivity of the filler, the filler content, the polyimide structure, the thermal diffusivity of the polyimide, the polyimide content, etc.

[0075] <<Filler>> The composition of the present invention may contain a filler. When a filler is contained, the filler is preferably thermally conductive. The filler may be electrically insulating, semiconducting, or conductive. The degree of electrical insulation and conductivity is appropriately selected depending on the design and purpose. For example, in the case of an electrically insulating filler, the lower limit of the volume resistivity of the filler is 1.0 × 10 11 It is preferable that the resistance is 5.0×10 Ω·cm or more. 11 It is more preferable that the resistance is Ω·cm or more, and 1.0×10 12 The upper limit of the volume resistivity is not particularly limited, but is, for example, 1.0×10 18 It is preferably Ω·cm.

[0076] On the other hand, in the case of a semiconductor or conductive filler, the lower limit of the volume resistivity of the filler is not particularly limited, but for example, 1.0 × 10 -7 The upper limit of the volume resistivity is preferably 1.0×10 11 It is preferably less than Ω·cm.

[0077] The thermal diffusivity of the filler is, for example, 1.0 × 10 -6 m 2 s -1 That is 2.0 x 10 -6 m 2 s -1 It is preferable that the value is 5.0×10 or more. -6 m 2 s -1 The upper limit of the thermal diffusivity of the filler is not particularly limited, but it is preferably 1.0×10 -4 m 2 s -1 It is preferable that:

[0078] The density of the filler is, for example, 4.0 g / cm 3 less than or equal to 3.0 g / cm 3 The lower limit of the density of the filler is not particularly limited, but is, for example, 1.0 g / cm 3In addition, when the filler is a porous or hollow particle having voids or cavities, the density of the filler in this specification means the density of the solid content of the components constituting the filler.

[0079] Preferably, the filler contains an electrically insulating material. Examples of electrically insulating filler materials include electrically insulating ceramics composed of nitrogen compounds, oxygen compounds, silicon compounds, boron compounds, carbon compounds, and composite compounds thereof. Examples of nitrogen compounds include boron nitride, aluminum nitride, and silicon nitride. Examples of oxygen compounds include metal oxides such as aluminum oxide (alumina), magnesium oxide (magnesia), zinc oxide, silicon oxide (silica), beryllium oxide, titanium oxide (titania), copper oxide, and cuprous oxide. Examples of silicon compounds and carbon compounds include silicon carbide. Examples of boron compounds include metal borides such as titanium boride. Other carbon compounds include carbon matrix materials with predominantly σ-bonding, such as diamond. Examples of the composite compounds include mineral ceramics such as magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, bentonite, and pyroferrite. The electrically insulating filler material may also be a metal hydroxide such as magnesium hydroxide or aluminum hydroxide.

[0080] Among these, from the viewpoint of thermal conductivity, it is preferable that the filler material contains at least one of ceramics made of nitrogen compounds, ceramics made of metal oxides, and metal hydroxides. The filler material preferably contains at least one of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide, and aluminum hydroxide. In particular, it is particularly preferable that the filler material is at least one of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide. Note that boron nitride may have any structure, such as c-BN (cubic crystal structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), r-BN (rhombohedral crystal structure), or t-BN (turbostratic structure). Boron nitride can be spherical or flaky, and either can be used.

[0081] Examples of conductive filler materials include carbon matrix materials with predominantly π-bonds, such as graphite, carbon black, graphite, carbon fibers (pitch-based, PAN-based), carbon nanotubes (CNTs), and carbon nanofibers (CNFs). Such filler materials may also include metals such as silver, copper, iron, nickel, aluminum, and titanium, as well as alloys such as stainless steel (SUS). Furthermore, such filler materials may also include conductive metal oxides, such as zinc oxide, doped with different elements, and conductive ceramics, such as ferrite.

[0082] The filler may be a semiconductor or conductive thermally conductive particle coated or surface-treated with an electrically insulating material such as silica. This configuration facilitates individual control of the thermal conductivity and electrical insulation, making it easy to adjust the thermal conductivity and electrical insulation. For example, methods for forming a silica film on the surface include the water glass method and the sol-gel method.

[0083] These fillers can be used alone or in combination of two or more. The filler may have a variety of shapes, such as fiber, plate, scale, rod, sphere, tube, curved plate, needle, etc.

[0084] The filler may be subjected to a surface treatment such as a silane coupling treatment, a titanate coupling treatment, an epoxy treatment, a urethane treatment, or an oxidation treatment. Examples of surface treatment agents used for the surface treatment include polyols, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamines, stearic acid, organosiloxanes, zirconium oxide, hydrogen dimethicone, silane coupling agents, and titanate coupling agents. Among these, silane coupling agents are preferred.

[0085] Regarding the size of the filler, the average primary particle diameter of the filler is preferably 0.01 to 30 μm. The lower limit is more preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.5 μm or more. The upper limit is more preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. The "average primary particle diameter" of the filler can be determined by observing the filler in a dispersion liquid with a transmission electron microscope (TEM) and observing the non-aggregated portions of the filler particles (primary particles). Specifically, a transmission electron microscope photograph of the filler primary particles is taken using a transmission electron microscope, and the photograph is then processed using an image processing device to measure the particle size distribution of the filler. The number-based arithmetic mean diameter calculated from the particle size distribution is then used as the "average primary particle diameter" of the filler. For example, an electron microscope (H-7000) manufactured by Hitachi, Ltd. is used as the transmission electron microscope, and Luzex AP manufactured by Nireco Corporation is used as the image processing device.

[0086] The filler may contain a granular mixture of at least two particle groups with different average primary particle diameters. The "average primary particle diameter" of a particle group is determined using the same method as the "average primary particle diameter" of the filler. This configuration results in smaller particles being embedded between larger particles, reducing the spacing between the fillers and increasing the number of contact points compared to a filler containing only a single diameter. This improves thermal conductivity. For example, when two particle groups with different average primary particle diameters are mixed, two peaks are observed in the particle size distribution of the filler containing these particle groups. Therefore, by checking the number of peaks in the particle size distribution of the filler, it is possible to determine how many types of particle groups with different average primary particle diameters are contained in the granular mixture of the filler.

[0087] When the particle size distribution of the filler has multiple peaks, the peak particle size ratio (the ratio of particle sizes corresponding to the peak apexes) between at least two peaks is preferably 1.5 to 50. The lower limit is preferably 2 or more, more preferably 4 or more. The upper limit is preferably 40 or less, more preferably 20 or less. When the peak ratio is within the above range, it is possible to prevent large-diameter fillers from becoming coarse particles, while allowing small-diameter fillers to easily occupy the spaces between the large-diameter fillers. Furthermore, between at least two peaks, the peak intensity ratio of the large-diameter peak to the small-diameter peak is preferably 0.2 to 5.0. The lower limit is preferably 0.3 or more, more preferably 0.5 or more. The upper limit is preferably 4.0 or less, more preferably 3.0 or less.

[0088] The aspect ratio of the filler is preferably 2 or more, more preferably 4 or more, and particularly preferably 5 or more. The upper limit of this aspect ratio is preferably 1000 or less, more preferably 500 or less, and particularly preferably 100 or less. The "aspect ratio" of a filler is the ratio of the minimum length to the maximum length among the three-dimensional lengths (maximum length / minimum length).

[0089] In addition, it is also one of the preferred embodiments of the present invention to use two or more fillers made of different materials. For example, a combination of boron nitride and aluminum oxide, or a combination of aluminum nitride and aluminum oxide is preferred. Also preferred are combinations of two or more fillers made of the same material but with different aspect ratios, and combinations of two or more fillers made of different materials but with different aspect ratios.

[0090] The content of the filler in the composition is preferably 1% by volume or more, more preferably 5% by volume or more, particularly preferably 10% by volume or more, and most preferably 20% by volume or more, based on the volume of the total solids of the composition. From the viewpoint of lithographic processability, the content is more preferably 85% by volume or less, even more preferably 81% by volume or less, particularly preferably 75% by volume or less, and most preferably 60% by volume or less, based on the volume of the total solids of the composition. The content of the filler in the composition is preferably 10% by mass or more, more preferably 30% by mass or more, based on the mass of the total solids of the composition. From the viewpoint of lithographic processability, the upper limit of this percentage is preferably 90% by mass or less, particularly preferably 70% by mass or less. By considering processability in addition to thermal conductivity and electrical insulation in this way, a heat-conducting layer with high thermal conductivity and electrical insulation can be formed in a desired position and pattern.

[0091] The proportion of particles having an average primary particle size of 0.5 to 15 μm in the filler is preferably 50% by mass or more, more preferably 80% by mass or more. The upper limit of this proportion can be set to 100% by mass or 99% by mass or less. From the viewpoint of processability by lithography, this proportion is preferably 99% by mass or less, more preferably 95% by mass or less.

[0092] As described above, the filler can be used alone or in combination of two or more types, and when two or more types of fillers are contained, the total amount thereof is preferably within the above range.

[0093] The polyimide-containing portion is preferably an insulating member. The insulating property (electrical resistance) of the polyimide-containing portion is not particularly limited, but the volume resistivity is preferably 1×10 15 It is preferable that the resistance is Ω·cm or more, and 1×10 16 It is more preferable that the resistivity is Ω·cm or more. There is no upper limit, but it is preferably 1×10 19 In practice, the dielectric strength is Ω·cm or less. The breakdown voltage is preferably 1 kV / mm or more, and more preferably 10 kV / mm or more. There is no particular upper limit, but in practice, the dielectric strength is 1000 kV / mm or less. In this specification, measurements of volume resistivity and breakdown voltage etc. are in accordance with JIS C2151:2006 and JIS C2318:2007.

[0094] The glass transition temperature of the polyimide-containing portion is preferably 250° C. or lower, more preferably 230° C. or lower, and even more preferably 220° C. or lower. There is no particular lower limit to the glass transition temperature, but it is preferably 120° C. or higher.

[0095] The difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more, preferably 6% or more. In another preferred embodiment of the present invention, the difference in cyclization rate is 10% or more. In the present invention, the cyclization rate of the polyimide is measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak at 1370 cm due to the imide structure was observed. -1 Next, the polyimide is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again to obtain the peak intensity P1 around 1370cm. -1The peak intensity P2 near the peak intensity P1 is measured. The cyclization rate of the polyimide can be calculated using the obtained peak intensities P1 and P2 based on the following formula: Cyclization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0096] The cyclization rate of the polyimide in the polyimide-containing precursor part before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%. The cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 91 to 100%, more preferably 94 to 100%, and even more preferably 97 to 100%.

[0097] When the substrate B includes a second polyimide-containing precursor portion, the difference between the cyclization rate of the polyimide in the second polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide contained in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 5% or more, more preferably 6% or more. In another preferred embodiment of the present invention, the difference in cyclization rate is 10% or more. When the substrate B has a second polyimide-containing precursor portion, the cyclization rate of the polyimide in the second polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%.

[0098] <Annealing process> The annealing step is a heating step that may be incorporated after a bonding step (eg, bonding with a flip-chip bonder). The annealing step can increase the peel resistance of the bond. The heating means is not particularly limited, but for example, a heating device such as a hot plate or an oven can be used. The heating temperature in the annealing step is preferably equal to or lower than the bonding temperature in the bonding step. The heating temperature in the annealing step is preferably 180 to 440°C, more preferably 200 to 350°C, and even more preferably 210 to 260°C. The heating temperature in the annealing step may be determined in consideration of the bonding temperature in the bonding step and the heating temperature in the heating step. The difference between the bonding temperature in the bonding step and the heating temperature in the annealing step (bonding temperature in the bonding step - heating temperature in the annealing step) is preferably 10°C or more. There is no particular upper limit, but for example, it is preferably 250°C or less, and more preferably 200°C or less. When the above-mentioned heating step is carried out, the heating temperature in the annealing step is preferably equal to or higher than the heating temperature (maximum heating temperature) in the above-mentioned heating step. The difference between the heating temperature in the annealing step and the heating temperature in the heating step (heating temperature in the annealing step - heating temperature in the heating step) is preferably 10° C. or more, more preferably 30° C. or more. There is no particular upper limit, but for example, it is preferably 250° C. or less, more preferably 150° C. or less. The heating time in the annealing step is preferably equal to or longer than the bonding time in the bonding step. The heating time in the annealing step (heating time at the above heating temperature) is preferably 1 hour or more. There is no particular upper limit to the heating time, but it is preferably 10 hours or less, and more preferably 5 hours or less. The difference between the heating time in the annealing step and the heating time in the bonding step (heating time in the annealing step - heating time in the bonding step) is preferably 30 minutes or more. Although there is no particular upper limit, it is preferably 10 hours or less, and more preferably 5 hours or less. The atmosphere during heating can be appropriately selected from those available with the heating equipment, such as air, nitrogen, or vacuum. The atmospheric pressure is not particularly limited, but is preferably 1 atmosphere or less, and more preferably 1 atmosphere ±0.1 atmosphere. 1 atmosphere means 101,325 Pa. For example, the reaction can be carried out at atmospheric pressure without pressurizing or depressurizing. The imidization rate after the annealing step is preferably, for example, 98% or more. There is no particular upper limit, and it is also preferable that it be, for example, 100%.

[0099] [Other steps] The method for producing a bonded body of the present invention does not preclude the inclusion of other steps between the steps specified above. While the bonding step has been described mainly as an example in which substrate A and substrate B are bonded face-to-face, it is also possible to use a configuration in which a plurality of substrates B are arranged in parallel with substrate A and bonded together. Alternatively, a configuration in which substrates A and B having a suitable thickness are placed side by side and bonded together may also be used.

[0100] <Example of manufacturing method of bonded body> An example of a method for producing a bonded body will be described below with reference to the drawings. FIG. 2 is a process explanatory diagram showing, in cross section, a process (part) when bonding substrates in a method for producing a bonded body according to one embodiment of the present invention. First, a substrate A (base substrate) 1 is prepared, in which an electronic circuit region 8 is disposed on a silicon wafer 1x and electrodes 31 (wiring terminals A) are attached thereto (FIG. 2(a)). An electronic circuit 81 made of a conductor or semiconductor is already formed within the electronic circuit region 8 of the substrate A1. There are no particular restrictions on the method for forming the electronic circuit, and it can be formed by a standard method. There are also no particular restrictions on the structure and materials of the electronic circuit, and examples include transistors and a wiring structure that connects them to electrodes.

[0101] A resin composition is applied to the electrode-formed surface (surface having an electronic circuit region) P0 of the substrate A1 to form a member (resin composition layer) 4 made of the resin composition (FIG. 2(b)). In this state, the resin composition layer may be heated and dried (drying step). After drying, the resin composition layer 4 may be patterned by photolithography, ion sputtering, or the like.

[0102] In this embodiment, the resin composition layer 4 is then heated to promote cyclization, thereby partially cyclizing (curing) the polyimide precursor to form a polyimide-containing precursor part 41 (FIG. 2(c)). This results in a polyimide-containing precursor part-disposed substrate 1y in which the polyimide-containing precursor part 41 is disposed on the substrate A1. As in this example, the polyimide-containing precursor part 41 may shrink due to curing compared to the resin composition layer 4. Although the amount of shrinkage is shown somewhat exaggerated in the drawing, the shrinkage rate is not particularly limited, and may be smaller, or may not shrink at all due to curing. Furthermore, although the substrate A shown in the drawing has only the electrode 31 as the wiring terminal A, a conductive path may be formed on the electrode 31. The conductive path may be formed in the substrate A from the beginning, or the polyimide-containing precursor portion may be patterned before curing, and the conductive path may be formed in the patterned portion by plating or the like.

[0103] In the polyimide-containing precursor portion-disposed substrate 1y of this embodiment, the heights h1 and h2 of the electrodes 31 vary. Furthermore, the surface 4a of the polyimide-containing precursor portion is also wavy and not flat. In this embodiment, planarization is performed to eliminate such variations in the height of the electrodes 31, expose their tip surfaces, and also planarize the surface of the polyimide-containing precursor portion. It is believed that such planarization improves the adhesion of the substrate. Furthermore, it is believed that the bonding between the wiring terminals is improved even without forming a conductive path.

[0104] 3(a) to 3(c) each show a polyimide-containing precursor portion-disposed substrate (laminate) 1z after planarization. The tip 31a of the electrode 31 is exposed on the surface 4b of this polyimide-containing precursor portion, and the entire surface 4b of the polyimide-containing precursor portion is planarized. Figure 3(a) shows an example of an embodiment in which the height of the electrode 31 and the height of the surface 4b of the polyimide-containing precursor are the same height, Figure 3(b) shows an example of an embodiment in which the height of the surface 4b of the polyimide-containing precursor is lower than the height of the electrode 31, and Figure 3(c) shows an example of an embodiment in which the height of the surface 4b of the polyimide-containing precursor is higher than the height of the electrode 31.

[0105] A substrate B is prepared separately from the laminate (planarized substrate having a polyimide-containing precursor portion) 1z (FIG. 4(a)). The substrate B2 includes a silicon wafer 2x having a through-hole electrode 2y, a circuit wiring region 8 having a circuit wiring 81 disposed thereon, and an electrode 32 (wiring terminal B) formed within the circuit wiring region 8. In this embodiment, a second polyimide-containing precursor part 42 is also formed on the surface of substrate B having wiring terminal B, and its surface 2a is planarized in the same manner as the surface of polyimide-containing precursor part 41 on substrate A. The formation and planarization of the second polyimide-containing precursor part 42 can be performed by the same method as the formation and planarization of the polyimide-containing precursor part 41. In this way, the surfaces of the polyimide-containing precursor portion 41 and electrode 31 of substrate A and the surfaces of the second polyimide-containing precursor portion 42 and electrode 32 of substrate B are both flattened, thereby improving electrical connectivity even when there is no conductive path as in this embodiment. At this time, alignment (positioning) is performed so that the electrode 31 portion of the laminate comes into contact with the electrode 32 provided on the substrate B2. Here, if at least one of the polyimide-containing precursor part 41 and the second polyimide-containing precursor part 42 contains a migration inhibitor, even if a positional shift occurs in this alignment, it is possible to suppress the migration of metal from the electrode 31 (electrode 32) to the polyimide-containing precursor part 41 (second polyimide-containing precursor part 42), thereby improving the voltage resistance performance. In the wiring terminal B, a conductive path may also be formed on the electrode 32. The conductive path may be formed in the substrate B from the beginning, or the second polyimide-containing precursor part may be patterned before being cured, and the conductive path may be formed in the patterned part by plating or the like.

[0106] Next, in this embodiment, the aligned substrate B2 and the laminate 1z are bonded together at the bonding surface P1 via the polyimide-containing precursor part 41 and the second polyimide-containing precursor part 42 (FIG. 4(b)). This forms a bonded body 100 in which the two substrates are bonded together. In the bonded body 100, the electrode 31 and the electrode 32 are electrically bonded together (bonding step). At the same time, the polyimide-containing precursor portion 41 is softened by heating, and the polyimide-containing precursor portion surface 4b of the laminate 1z is bonded to the surface 2a of the substrate B (the planarized surface of the second polyimide-containing precursor portion 42), thereby forming the bonded body 100. In the bonded body 100, a polyimide-containing portion 51 is formed from the polyimide-containing precursor portion 41 and the second polyimide-containing precursor portion 42. The polyimide contained in this polyimide-containing portion is further cyclized by the heating during the bonding process. Therefore, the difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion 41 before the bonding process and the cyclization rate of the polyimide in the polyimide-containing portion 51 formed at the bonded portion after the bonding process is 5% or more. This allows electrical connection between substrate A and substrate B, and also allows the two to be firmly fixed together due to the anchor effect described above.

[0107] In a preferred embodiment of the present invention, the polyimide-containing precursor portion surface 4b and the second polyimide-containing precursor portion surface 2a of the laminate 1z have high flatness, so that a dense and accurate contact state with the substrate B2 can be achieved at the contact surface. By achieving a denser and more accurate contact state, voids that tend to occur at the contact surface can be effectively suppressed.

[0108] (zygote) The bonded body of the present invention is a bonded body obtained by the method for producing a bonded body of the present invention. The bonded body of the present invention can be suitably used in applications such as the device of the present invention described below.

[0109] (Method of manufacturing laminate) The method for producing a laminate of the present invention includes the steps of: preparing a substrate C having two or more surfaces each having a wiring terminal; preparing a plurality of substrates D each having a surface each having a wiring terminal; forming a polyimide-containing precursor portion on the surface each having the wiring terminal of at least one of the substrates C and D; and joining the surface of the substrate D having the wiring terminal to each of at least two of the surfaces each having the wiring terminal of the substrate C, wherein the polyimide-containing precursor portion is present at all of the joints in the joining step, and at least one of the joints has a difference of 5% or more between the cyclization rate of polyimide in the polyimide-containing precursor portion joined at the joint before the joining step and the cyclization rate of polyimide in the polyimide-containing portion formed at the joint after the joining step.

[0110] <Step of preparing substrate C> The method for producing a bonded body of the present invention includes a step of preparing a substrate C having two or more surfaces provided with wiring terminals. In the step of preparing the substrate C, the substrate C may be manufactured by a known method or may be obtained by purchasing or other means. In the method for producing a laminate of the present invention, the material used for the substrate C and the wiring terminal provided on the substrate C can be the same as the material used for the substrate A and the wiring terminal A described above, and the preferred embodiments are also the same. Furthermore, the substrate C may be a wafer or a chip, and the preferred embodiments thereof are the same as those for the substrate A.

[0111] <Step of Preparing Substrate D> In the step of preparing the substrate D, the substrate D may be manufactured by a known method or may be obtained by purchasing or other means. As the substrate D in the method for producing a laminate of the present invention, a substrate similar to the substrate B described above can be used, and the preferred embodiments are also similar. Furthermore, the substrate D may be a wafer or a chip, and the preferred embodiments thereof are the same as those for the substrate B.

[0112] <Polyimide-containing precursor portion forming step> In the polyimide-containing precursor portion forming step, a polyimide-containing precursor portion is formed on the surface of at least one of the substrates C and D. Here, when two substrates D (let's say substrate D1 and substrate D2) are bonded to substrate C, polyimide-containing precursor portions may be formed on the two surfaces of substrate C to which substrate D1 and substrate D2 are bonded, or polyimide-containing precursor portions may be formed on the surface of substrate C to which substrate D1 is bonded and the surface having the wiring terminals of substrate D2, or polyimide-containing precursor portions may be formed on the surfaces having the wiring terminals of substrate D1 and substrate D2, or polyimide-containing precursor portions may be formed on all of the surfaces having the wiring terminals of substrate C, substrate D1, and substrate D2. A preferred embodiment of the method for forming the polyimide-containing precursor portion is the same as the preferred embodiment of the method for forming the polyimide-containing precursor portion in the above-described method for producing a bonded body of the present invention.

[0113] <Joining process> The method includes a bonding step of bonding a surface of the substrate D having the wiring terminal to each of at least two of the surfaces of the substrate C having the wiring terminal, wherein the polyimide-containing precursor portion is present at all of the bonding portions in the bonding step, and at least one of the bonding portions has a difference of 5% or more between the cyclization rate of the polyimide in the polyimide-containing precursor portion bonded at the bonding portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonding portion after the bonding step. Here, when two substrates D (let's say substrate D1 and substrate D2) are bonded to substrate C, the bonding process may be performed in two steps, with substrate D1 being bonded to substrate C and then substrate D2 being bonded to substrate C, or the bonding process may be performed all at once. Furthermore, another substrate may be further bonded to the surface of substrate D that is not bonded to substrate C. This bonding step may also be performed in separate steps or may be performed all at once.

[0114] The difference in the cyclization rate is 5% or more, preferably 6% or more. In one preferred embodiment of the present invention, the difference in the cyclization rate is 10% or more. From the viewpoint of adhesion, the difference in the cyclization rate at all junctions is preferably 5% or more, more preferably 6% or more, and in one preferred embodiment of the present invention, the difference in the cyclization rate is 10% or more.

[0115] The cyclization rate of the polyimide in the polyimide-containing precursor part before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%. The cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 91 to 100%, more preferably 94 to 100%, and even more preferably 97 to 100%.

[0116] <Annealing process> The method for producing a laminate of the present invention may further include an annealing step after the bonding step. The details of the annealing step are the same as those of the annealing step in the method for producing a bonded body of the present invention.

[0117] [Other steps] The method for producing a bonded body of the present invention does not preclude the inclusion of other steps between the steps specified above.

[0118] (Laminate) The laminate of the present invention is a laminate obtained by the laminate manufacturing method of the present invention. The laminate of the present invention can be suitably used for applications such as the device of the present invention described below.

[0119] (Device and its manufacturing method) The device according to the present invention comprises the bonded body according to the present invention or the laminate according to the present invention. The method for producing a device of the present invention includes the method for producing a bonded body of the present invention or the method for producing a laminate of the present invention. The device according to the present invention includes a semiconductor device, an electronic device, etc., and is preferably a semiconductor device or an electronic device. Examples of the device include those described in "Illustrated: All about Cutting-Edge Semiconductor Packaging Technology" edited by Semiconductor New Technology Research Association, Kogyo Chosakai, pp. 8-19, 110-114, 160-165, and "Illustrated: All about Surface Treatment Technology" edited by Kanto Gakuin University Surface Optics Research Institute, Kogyo Chosakai, pp. 32-41, 56-59. Specifically, the polyimide-containing portion may be used as an adhesive film that replaces underfill between chips, or as a die-bonding film that fixes chips. The method for manufacturing a bonded body and a laminate of the present invention can be widely applied to a variety of other applications, such as mounting LED (light emitting diode) elements, mounting optical elements for flat panel displays, and mounting power semiconductor packages. Furthermore, for example, the method for manufacturing a bonded body and the method for manufacturing a laminated body of the present invention can also be suitably used for three-dimensional mounting of semiconductor elements provided with through electrodes (TSV: Through silicon via). FIG. 5 is a cross-sectional view schematically illustrating a three-dimensionally mounted device. In this embodiment, a laminate 101, in which multiple semiconductor elements (semiconductor chips) 101a to 101d are stacked, is disposed on a wiring substrate 120. Each of the multiple semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate. The laminate 101 has a structure in which a semiconductor element 101a without through electrodes is flip-chip connected to semiconductor elements 101b to 101d with through electrodes 102b to 102d. Connection pads on the semiconductor elements with through electrodes are connected by metal bumps 103a, 103b, and 103c such as solder bumps. A resin layer 110 is formed in the gaps between the semiconductor elements 101a to 101d. The method for manufacturing a bonded body of the present invention can be used to manufacture this laminate. That is, for example, at least one (preferably all) of the resin layers 110 can be a polyimide-containing portion in the above-described method for manufacturing a bonded body of the present invention or the method for manufacturing a laminate of the present invention. A surface electrode 120a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the laminate (substrate / substrate laminate) 101. One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d facing the rewiring layer 105 via a metal bump 103d, such as a solder bump. The other end of the rewiring layer 105 is connected to a surface electrode 120a of the wiring substrate via a metal bump 103e, such as a solder bump. A resin layer 110a is formed between the insulating layer 115 and the laminate 101. The method for manufacturing a bonded body or a laminate of the present invention can also be used to bond this insulating layer 115 and the laminate 101. That is, for example, the resin layer 110a can be the polyimide-containing portion described above. A resin layer 110b is formed between the insulating layer 115 and the wiring substrate 120. The method for manufacturing a bonded body of the present invention or the method for manufacturing a laminate of the present invention can also be used to bond this insulating layer 115 and wiring board 120. That is, for example, the resin layer 110b can be the polyimide-containing portion described above.

[0120] (Polyimide-containing precursor portion-forming composition) The polyimide-containing precursor part-forming composition of the present invention is used in a method for producing a bonded body, the method including the steps of: preparing a substrate A having a surface with wiring terminals; forming a polyimide-containing precursor part on the surface of the substrate A having the wiring terminals; preparing a substrate B having a surface with wiring terminals; and bonding the surface of the substrate A having the polyimide-containing precursor part with the surface of the substrate B having the wiring terminals, wherein the polyimide-containing precursor part is a member formed from the polyimide-containing precursor part-forming composition, and the difference between the polyimide cyclization rate in the polyimide-containing precursor part before the bonding step and the polyimide cyclization rate in the polyimide-containing part formed at the bonded part after the bonding step is 5% or more. Here, the method for producing the bonded body is the same as the method for producing the bonded body of the present invention described above, and the preferred embodiments are also the same. The polyimide-containing precursor portion-forming composition of the present invention is synonymous with the polyimide-containing precursor portion-forming composition used to form the polyimide-containing precursor portion in the above-described method for producing a bonded body or method for producing a laminate of the present invention, and preferred embodiments are also the same.

[0121] In the use of the composition, the difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the joining step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the joint after the joining step is 5% or more, preferably 6% or more. In another preferred embodiment of the present invention, the difference in cyclization rate is 10% or more. The cyclization rate of the polyimide in the polyimide-containing precursor part before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%. In the use of the composition, the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 91 to 100%, more preferably 94 to 100%, and even more preferably 97 to 100%.

[0122] Hereinafter, each component contained in the polyimide-containing precursor part-forming composition (resin composition) of the present invention will be described in detail. The polyimide-containing precursor portion-forming composition of the present invention preferably contains a polyimide precursor and a solvent. The polyimide-containing precursor part-forming composition of the present invention preferably further contains a photosensitive compound. Examples of the photosensitive compound include a photopolymerization initiator and a photoacid generator, and a photopolymerization initiator is preferred.

[0123] <Specific resin> The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of polyimides and polyimide precursors, and more preferably contains a polyimide precursor. The specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described below, and more preferably contains both the radical polymerization initiator described below and a radical crosslinking agent described below. Furthermore, if necessary, the resin composition of the present invention may contain a sensitizer described below. For example, a negative-tone photosensitive film can be formed from such a resin composition of the present invention. The specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. From such a resin composition of the present invention, for example, a chemically amplified positive-working photosensitive film or negative-working photosensitive film is formed.

[0124] [Polyimide precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2). [ka] In formula (2), A 1 and A 2each independently represents an oxygen atom or -NH-; R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0125] A in equation (2) 1 and A 2 each independently represents an oxygen atom or —NH—, and preferably an oxygen atom. R in Equation (2) 111 represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, and particularly preferred is a group represented by -Ar-L-Ar-. wherein each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0126] R 111 is preferably derived from a diamine. Examples of diamines used in producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine preferably contains a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0127] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from combinations thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, or a group selected from -O-, -C(=O)-, -S-, or -SO2-; and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0128] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- and 1,3-diaminocyclopentane, 1,2-, 1,3-, and 1,4-diaminocyclohexane, 1,2-, 1,3-, and 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-Diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine methyldisiloxane, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl may be mentioned.

[0129] Additionally, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598 are also preferred.

[0130] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0131] R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the obtained organic film. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0132] Also, R 111From the viewpoint of i-line transmittance, is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferably a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of the above is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom in formula (2). R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

[0133] R in Equation (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. [ka] In formula (5), R 112 represents a single bond or a divalent linking group, and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, and -NHCO-, or a combination thereof; more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO2-; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0134] R 115 Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. 115 As a structure corresponding to the above, only one type of tetracarboxylic dianhydride residue may be contained, or two or more types may be contained. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [ka] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The same applies to the preferred range.

[0135] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 ',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0136] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0137] In equation (2), R 111 and R 115At least one of R may have an OH group. 111 Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0138] R in Equation (2) 113 and R 114 Each of R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. 113 and R 114 Preferably, at least one of R contains a polymerizable group, and more preferably, both of R contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0139] [ka]

[0140] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201 Examples of the alkylene group include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene; 1,2-butanediyl, 1,3-butanediyl, -CHCH(OH)CH-; and polyalkyleneoxy groups. Of these, alkylene groups such as ethylene and propylene, -CHCH(OH)CH-, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.

[0141] In equation (2), R 113 is a hydrogen atom, or R 114 When is a hydrogen atom, the polyimide precursor may form a counter 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.

[0142] In equation (2), R 113 and R 114 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0143] The polyimide precursor preferably has fluorine atoms in its structure, and the fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0144] To improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as diamines.

[0145] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, and R 111 and R 112 each independently represents a divalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0146] A 1 , A 2 , R 111 , R 113 and R 114 are each independently A in formula (2). 1 , A 2 , R 111 , R113 and R 114 The same applies to the preferred range. R 112 is R in Equation (5). 112 The same applies to the preferred range.

[0147] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0148] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0149] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The polyimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are within the above-mentioned ranges.

[0150] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at least 0.1 g in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyimide that dissolves at least 0.5 g is preferred, and a polyimide that dissolves at least 1.0 g is more preferred. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less. In addition, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In this specification, the term "main chain" refers to the relatively longest bonded chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to any other bonded chain.

[0151] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. The fluorine atom can be, for example, R 132 or R in the repeating unit represented by formula (4) described below 131 and R in the repeating unit represented by formula (4) described below is preferably included. 132 or R in the repeating unit represented by formula (4) described below 131 It is more preferable that the alkyl group is contained as a fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

[0152] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described below. 131 and R in the repeating unit represented by formula (4) described below is preferably included. 131 It is more preferable that the organic modified (poly)siloxane structure described below is contained in the above. The silicon atom or the organically modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0153] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is represented by R in the repeating unit represented by formula (4) described below. 132 or R in the repeating unit represented by formula (4) described below 131 and R in the repeating unit represented by formula (4) described below is preferably included. 132 or R in the repeating unit represented by formula (4) described below 131 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described below. 131 and R in the repeating unit represented by formula (4) described below is preferably included.131 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV):

[0154] [ka]

[0155] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0156] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CHCH(OH)CH-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0157] Among these, R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1). [ka] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R 21 represents the bonding site with the oxygen atom to which it is bonded. In the formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L are the same as those of the above-mentioned R 21 The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in the above. In formula (R1), X is preferably an oxygen atom. In the formulae (R1) to (R3), * has the same meaning as * in the formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0158] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0159] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0160] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond. Examples of polymerizable groups other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. The polymerizable group other than the group having an ethylenically unsaturated bond is preferably contained in, for example, R131 in the repeating unit represented by formula (4) described below. The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0161] -Polarity conversion group- The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is represented by R 113 and R 114 The acid-decomposable group is the same as that described above, and the preferred embodiments are also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described below. 131 , R 132 , contained in the terminals of polyimides, etc.

[0162] -Acid value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. Furthermore, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability. pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa is a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, values ​​listed in the "Revised 5th Edition Chemistry Handbook: Basics" edited by the Chemical Society of Japan may be referenced. Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

[0163] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group is, for example, R in the repeating unit represented by formula (4) described below. 132 or R in the repeating unit represented by formula (4) described below 131 It is preferred that the hydroxyl group is included in the formula (I). The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0164] 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 a repeating unit represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group. In the case where the polymerizable group is present, the polymerizable group is R 131 and R 132 or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4). Formula (4-2) [ka] R 134 and R 135 At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0165] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, and crosslinkable groups other than the above-mentioned group having an ethylenically unsaturated bond. R 131 represents a divalent organic group. The divalent organic group is R in formula (2). 111 The same examples are given, and the preferred ranges are also the same. Also, R 131Examples of the diamine include a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. 111 Examples include:

[0166] R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0167] Examples of diamines containing two or more ethylene glycol chains, two or more propylene glycol chains in one molecule include, but are not limited to, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0168] R 132 represents a tetravalent organic group. The tetravalent organic group is R in formula (2). 115 The same examples are given, and the preferred ranges are also the same. For example, R 115 The four bonds of the tetravalent organic group exemplified by the following are bonded to the four -C(=O)- moieties in the above formula (4) to form a fused ring.

[0169] Also, R 132 The R tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is an example.115 From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0170] R 131 and R 132 It is also preferable that at least one of R 131 Preferred examples of R 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, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18). 132 As such, the above (DAA-1) to (DAA-5) are more preferred examples.

[0171] The polyimide preferably has fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0172] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0173] In order to improve the storage stability of the resin composition, it is preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-8-aminonaphthalene. 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0174] -Ring closure rate- The imidization rate (also called ring closure rate) of the polyimide is preferably 70% or more, and more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. There is no particular upper limit to the imidization rate, but it is preferably 95% or less, and more preferably 90% or less. The imidization rate is measured by the method described above.

[0175] All polyimides are of the same type R 131 or R 132 and may contain a repeating unit represented by the above formula (4) containing two or more different types of R 131 or R 132 The polyimide may contain a repeating unit represented by the above formula (4), which includes: In addition to the repeating unit represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating unit represented by the above formula (2).

[0176] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used.

[0177] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (for example, breaking elongation), the weight-average molecular weight is particularly 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 polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersity of the polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimides as a single resin are each within the above-mentioned ranges.

[0178] [Method for producing polyimide precursors, etc.] The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, etc. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing a polyimide precursor, etc., it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately determined depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0179] -End-capping agent- In the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like to further improve storage stability. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of end-capping agents include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents. Furthermore, when capping the amino group at the resin terminal, it is possible to cap it with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0180] Furthermore, by using a compound having a structure that exhibits the property of generating a base as the end-capping agent, it is possible to introduce a structure that exhibits the property of generating a base into the end of the specific resin. Examples of such end-capping agents that can be used include compounds having a structure that exhibits the property of generating a base and a reactive group such as a hydroxy group, a thiol group, an amino group, a carboxy group, a carboxylic acid anhydride group, a carboxylic acid halide group, a sulfonic acid anhydride group, a sulfonic acid halide group, or a sulfonic acid carboxylic acid anhydride group. As the end-capping agent, for example, a compound having a structure exhibiting the property of generating one or more bases and one of the above-mentioned reactive groups can be used. Preferred embodiments of the structure exhibiting the property of generating a base are as described above.

[0181] The end-capping agent may be a compound represented by formula (T-1). By using such a compound to cap the ends, a structure that easily generates a base can be introduced at the end, which is thought to improve the elongation at break even when cured at low temperatures. [ka] In formula (T-1), L T represents a divalent organic group, Z 1 and Z 2 each independently represents an organic group; Z 1 and Z 2 may be bonded to form a ring structure.

[0182] In formula (T-1), L T is preferably a hydrocarbon group, which may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably either an aromatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group. L T The linking chain length (i.e., L T The number of atoms linking the two carbonyl groups bonded to (the minimum number of atoms) is preferably 2 to 4, and more preferably 2. In formula (T-1), Z 1 and Z 2 is Z in formula (3-1) 1 and Z 2 The same applies to the preferred embodiments. In particular, Z 1 , Z 2 and L T An embodiment in which at least one of the above has a polymerizable group is also one of the preferred embodiments of the present invention. Examples of the polymerizable group include a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, and the radical polymerizable group is preferred. The radical polymerizable group is preferably a group having an ethylenically unsaturated group, and examples thereof include a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, and a (meth)allyl group. Among these, the (meth)acryloxy group is preferred from the viewpoint of reactivity. These polymerizable groups may be bonded directly to the nitrogen atom in formula (T-1) or may be bonded via a linking group such as a hydrocarbon group (for example, an alkylene group).

[0183] -Solid precipitation- The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a polyimide precursor or the like. To improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0184] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

[0185] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R 115 ) preferably contains two or more kinds of polyimide precursors with different

[0186] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, a polymerizable compound having a molar content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0187] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. In addition, a preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low. In this embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0188] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound.

[0189] In particular, the resin composition of the present invention preferably contains a polymerizable compound having a ring structure. The ring structure may be an aliphatic ring structure, an aromatic ring structure, or a ring structure that is a combination of these, but preferably contains an aliphatic ring structure. The aromatic ring structure may be either an aromatic hydrocarbon ring structure or an aromatic hetero ring structure, but an aromatic hydrocarbon ring structure is preferred, and a benzene ring structure is more preferred. The aliphatic ring structure may be an aliphatic hydrocarbon ring structure or an aliphatic heterocyclic structure, but is preferably an aliphatic hydrocarbon ring structure. Specific examples of the ring structure contained in the polymerizable compound containing a ring structure include a cyclohexane ring, a norbornene ring, an isonorbornene ring, a dicyclopentane ring, an adamantane ring, a polyphenyl ring, a fluorene ring, and an acenaphthyl ring. The number of ring structures in the polymerizable compound having a ring structure is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. Examples of the polymerizable group in the polymerizable compound having a ring structure include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxazolyl group, and a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred. The number of polymerizable groups in the polymerizable compound having a ring structure is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 2.

[0190] The resin composition of the present invention preferably contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher. The glass transition temperature (Tg) of the homopolymer is measured, for example, by a differential scanning calorimeter in accordance with ASTM D3418-8. Although the glass transition temperature (Tg) varies depending on the molecular weight, the variation in Tg due to the molecular weight is negligible if the weight-average molecular weight is 10,000 or more. The glass transition temperature is preferably at least 210° C., and more preferably at least 220° C. The upper limit of the glass transition temperature is not particularly limited, but can be set to, for example, 350° C. or lower. By including a polymerizable compound having such a high glass transition temperature, the cyclization rate of the polyimide during the formation of the polyimide-containing precursor portion can be reduced, which may make it easier to adjust the difference in cyclization rate between the polyimide-containing portion obtained after the subsequent bonding step and the polyimide-containing portion obtained after the bonding step.

[0191] The polymerizable compound may be a radical crosslinking agent or other crosslinking agent.

[0192] [Radical crosslinking agent] The resin composition of the present invention 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 having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0193] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 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 ethylenically unsaturated bonds. In addition, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.

[0194] 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.

[0195] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. For specific examples, see paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0196] The radical crosslinking agent is also 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 compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0197] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0198] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), as well as compounds in which the (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these compounds can also be used.

[0199] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Corporation; SR-209, 231, and 239, difunctional methacrylates having four ethyleneoxy chains, manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.; and urethane acrylate. Examples of such an agent include Ligomer UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmer PME400 (manufactured by NOF Corporation).

[0200] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A No. 63-277653, JP-A No. 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0201] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0202] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0203] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the resin composition. 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, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain. In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product). Examples of the monofunctional radical crosslinking agent 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; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at normal pressure are also preferred as the monofunctional radical crosslinking agent. Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0204] When a radical crosslinking agent is contained, its content is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0205] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0206] [Other crosslinking agents] The resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used.In addition, oligomers formed by self-condensation of the methylol groups of these compounds may also be used. As the amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0207] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the compound is preferably 1,500 or less, and more preferably 180 to 1,200.

[0208] [ka]

[0209] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0210] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0211] [ka]

[0212] In the formula, X represents a single bond or a divalent organic group, and each R 104 each independently represents an alkyl group or an acyl group, and R 103represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, -C(R 4 )2COOR 5 A group represented by (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is eliminated by the action of an acid. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. A group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have known substituents within the range in which the effects of the present invention can be obtained.

[0213] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0214] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0215] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. The preferred embodiments of the above compound are the same as the preferred embodiments of the above crosslinking agent U, except that the polymerizable group is not a radical polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.

[0216] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compound is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0217] [ka]

[0218] [ka]

[0219] [ka]

[0220] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be commercially available or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0221] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0222] Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea; propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; Examples include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0223] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0224] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0225] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0226] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0227] -Epoxy compounds (compounds containing epoxy groups)- The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in low-temperature curing of the resin composition of the present invention and suppressing warpage.

[0228] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0229] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) BEO-20E, Likaresin (registered trademark) BEO-60E, Likaresin (registered trademark) HBE-100, Likaresin (registered trademark) DME-100, Likaresin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (all trade names, manufactured by ADEKA Corporation), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 0-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also preferably used.

[0230] [ka]

[0231] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0232] Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0233] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples that can be suitably used include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., and these may be used alone or in combination of two or more.

[0234] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that no degassing occurs during curing, and furthermore, they reduce thermal shrinkage and suppress the occurrence of warping.

[0235] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds, which may be used alone or in combination of two or more.

[0236] The content of the other crosslinking agent is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, even more preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %, based on the total solid content of the resin composition of the present invention. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total content thereof is preferably within the above range.

[0237] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat, and particularly preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations 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 range is preferred. Alternatively, it may be an activator that reacts in some way with a photoexcited sensitizer to generate active radicals.

[0238] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L·mol -1 ·cm -1 Preferably, the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0239] Any known photoradical polymerization initiator can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as 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, organic boron compounds, and iron arene complexes. For details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol.19, No.3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A are mentioned, the contents of which are also incorporated herein.

[0240] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0241] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0242] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF).

[0243] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF).

[0244] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0245] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0246] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232) compounds described in, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515, and the like, the contents of which are incorporated herein by reference.

[0247] Preferred oxime compounds include, for example, compounds having the following structure: 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-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In resin compositions, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group of >C=NOC(=O)- within the molecule.

[0248] [ka]

[0249] Commercially available products such as IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A) are also suitable. TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito ChemiX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Oxime compounds having the following structure can also be used. [ka]

[0250] Examples of the photoradical polymerization initiator include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. The contents of these compounds are incorporated herein by reference.

[0251] In addition, as the photopolymerization initiator, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, or an oxime compound having a hydroxyl group-containing substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, can also be used. The contents of these compounds are incorporated herein by reference.

[0252] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1It is also possible to use an oxime compound having the aromatic ring group Ar OX1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0253] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, R X2represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, R X3 ~R X14 each independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0254] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0255] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0256] Most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0257] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0258] More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, and at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

[0259] In addition, as the photoradical polymerization initiator, compounds described in paragraphs 0175 to 0179 of WO 2021 / 020359 can also be used, the contents of which are incorporated herein by reference.

[0260] Furthermore, the photoradical polymerization initiator may also be the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469, the contents of which are incorporated herein by reference.

[0261] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, WO-A-2015 / 004565, WO-A-2016-532675, paragraphs 0407 to 0412, and WO-A-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-A-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Application Publication No. 34963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0262] When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0263] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isodiethylaminobenzoate amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like. Other sensitizing dyes may also be used. For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of JP-A No. 2016-027357, the contents of which are incorporated herein by reference.

[0264] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0265] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0266] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0267] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be one type, or two or more types. When two or more types of chain transfer agents are used, the total amount thereof is preferably within the above range.

[0268] <Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator according to the present invention is not particularly limited, and known base generators can be used. Examples of known base generators that can be used include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Examples of non-ionic base generators include compounds represented by formula (B1) or formula (B2) described in paragraphs 0275 to 0285 of WO 2021 / 112189, compounds represented by formula (N1) described in paragraphs 0102 to 00162 of WO 2020 / 066416, and preferred base generators are thermal base generators described in paragraphs 0013 to 0041 of WO 2020 / 054226. The contents of these documents are incorporated herein.

[0269] Examples of the base generator include the following, but the present invention is not limited thereto.

[0270] [ka]

[0271] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0272] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0273] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0274] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0275] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Another preferred embodiment of the present invention is one in which the composition is substantially free of a base generator, which means that the content of the base generator is 0.1% by mass or less, more preferably 0.01% by mass or less, based on the total solid content of the composition of the present invention. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0276] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0277] 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, γ-valerolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 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.)), 2-alkoxypropionates, alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.), ... methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.), alkyl 3-alkoxy Suitable alkyloxypropionic acid alkyl esters include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionates (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), 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.

[0278] Suitable examples of ethers include 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 dimethyl 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.

[0279] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0280] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0281] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0282] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0283] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0284] Examples of 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, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0285] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0286] 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, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvents. In particular, from the viewpoint of storage stability of the resin composition, an embodiment in which γ-valerolactone is contained as a solvent is one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0287] From the viewpoint of coatability, the content of the solvent is preferably an amount that makes the total solids concentration of the resin composition of the present invention 5 to 80 mass %, more preferably an amount that makes it 5 to 75 mass %, even more preferably an amount that makes it 10 to 70 mass %, and even more preferably an amount that makes it 20 to 70 mass %. The content of the solvent may be adjusted depending on the desired thickness of the coating film and the coating method.

[0288] The resin composition of the present invention may contain only one solvent or two or more solvents. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0289] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers 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.

[0290] [Silane coupling agent] 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 Laid-Open 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 Laid-Open No. 2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0291] [ka]

[0292] 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 of suitable silanes 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-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent. Such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1). [ka] In formula (S-1), R S1 represents a monovalent organic group, and R S2 represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. R S1is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred. R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, and is preferably 1. Here, the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. As such oligomer type compounds, commercially available products can be used, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0293] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0294] In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935, the contents of which are incorporated herein by reference.

[0295] 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, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be one type, or two or more types. When two or more types are used, it is preferable that the total amount is within the above range.

[0296] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor, which makes it possible to effectively inhibit metal ions derived from the metal layer (metal wiring) from migrating into the film.

[0297] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (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, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, 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, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0298] Alternatively, an ion trapping agent that traps anions such as halogen ions can also be used.

[0299] Other migration inhibitors include, for example, the compounds described in paragraph 0304 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0300] Specific examples of the migration inhibitor include the following compounds: In addition, compounds E-2 to E-5 in the examples described below are also preferred specific examples.

[0301] [ka]

[0302] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solid content of the resin composition of the present invention.

[0303] The migration inhibitor may be one type only, or two or more types may be used. When two or more types of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0304] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

[0305] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine, the contents of which are incorporated herein by reference.

[0306] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the resin composition of the present invention.

[0307] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0308] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger to reduce performance changes over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, and primary amines, secondary amines, tertiary amines, and ammonium salts are preferred, with secondary amines, tertiary amines, and ammonium salts being more preferred. Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and aniline derivatives having a hydroxyl group and / or an ether bond. When the acid scavenger has an onium structure, it is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0309] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0310] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenyl ... diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

[0311] These acid scavengers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger. When the composition contains an acid scavenger, the content of the acid scavenger is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0312] The ratio of the acid generator to the acid scavenger used is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time after exposure until heat treatment, the molar ratio is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0313] <Other additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, provided that the effects of the present invention are achieved. By appropriately incorporating these components, film properties and other characteristics can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104 and 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0314] [Surfactant] As the surfactant, various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0315] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a surfactant-containing composition is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

[0316] Examples of fluorosurfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka]

[0317] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0318] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0319] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0320] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0321] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during the drying process after application.

[0322] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0323] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content thereof is preferably within the above range.

[0324] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. Adding a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0325] Examples of the thermal polymerization initiator include known azo compounds and known peroxide compounds. Examples of the azo compounds include azobis compounds. The azo compounds may be compounds having a cyano group or may be compounds not having a cyano group. Examples of the peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. As the thermal polymerization initiator, commercially available products can be used, and examples thereof include V-40, V-601, and VF-096 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and Perhexyl O, Perhexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percumyl D, Percumyl D-40, Percumyl D-40MB, Percumyl H, Percumyl P, and Percumyl ND manufactured by NOF Corporation.

[0326] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein by reference.

[0327] When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass %, and even more preferably 0.5 to 15 mass %. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0328] [Inorganic particles] The resin composition of the present invention may contain inorganic particles, such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, boron nitride, boron nitride nanotubes, boron carbon nitride, aluminum nitride, and silicon nitride.

[0329] The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size, which can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurements are difficult, centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method can also be used.

[0330] [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber, such as a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber. Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0331] In the present invention, the above-mentioned various ultraviolet absorbents may be used singly or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid mass of the composition of the present invention.

[0332] [Organotitanium Compounds] The resin composition of the present embodiment may contain an organotitanium compound. When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0333] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide resin compositions with good storage stability and produce good curing patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0334] Among these, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred as the organic titanium compound from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0335] When an organotitanium compound is added, the amount added is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount added is 0.05 part by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the composition has better storage stability.

[0336] [Antioxidants] The composition of the present invention may contain an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0337] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in a high-temperature, high-humidity environment, while by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, by interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0338] [Anti-aggregating agent] The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the anti-aggregation agent include sodium polyacrylate.

[0339] In the present invention, the anti-aggregating agent may be used alone or in combination of two or more. The composition of the present invention may or may not contain an anti-agglomerating agent. When the composition of the present invention contains an anti-agglomerating agent, the content of the anti-agglomerating agent is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.02% by mass to 5% by mass, relative to the total solid content by mass of the composition of the present invention.

[0340] [Phenol compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0341] In the present invention, the phenolic compounds may be used singly or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. When the composition of the present invention contains a phenolic compound, the content of the phenolic compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[0342] [Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified by introducing crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups.

[0343] In the present invention, the other polymer compounds may be used singly or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When the composition of the present invention contains other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid mass of the composition of the present invention.

[0344] <Characteristics of resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. 2 / s~12,000mm 2 / s is preferred, 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500 mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it is easy to obtain a highly uniform coating film. 2 / s or more, it is easy to apply it to a thickness required for an insulating film for rewiring, for example, and it is 12,000 mm 2 / s or less, a coating film with excellent surface condition can be obtained.

[0345] <Restrictions on substances contained in resin compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

[0346] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0347] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0348] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Among these, the content of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferred that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0349] A conventionally known container can be used as a container for storing the resin composition of the present invention. Furthermore, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A. [Example]

[0350] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0351] <Synthesis Example 1: Synthesis of Polymer P-1> 7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were placed in a reaction vessel, followed by 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 mL of γ-butyrolactone. 7.91 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the reaction ceased to generate heat, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) in 30 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 mL of γ-butyrolactone with stirring over 60 minutes. After stirring at room temperature for another 2 hours, 3 mL of ethyl alcohol was added and stirred for 1 hour. Then, 100 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a crude polymer precipitate. The crude polymer was collected by filtration and dissolved in 200 mL of tetrahydrofuran to produce a crude polymer solution. The crude polymer solution was added dropwise to 3 L of water to precipitate the polymer. The precipitate was collected by filtration and then vacuum dried to produce powdered polymer P-1. The weight average molecular weight (Mw) of this polymer was measured and found to be 23,000. Polymer P-1 is a resin having the following structure: The subscripts in parentheses represent the molar ratio of each repeating unit. [ka]

[0352] <Synthesis Example 2: Synthesis of Polymer P-2> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at 60 °C for 18 hours to produce the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled, and 16.12 g (135.5 mmol) of SOCl2 was added over 2 hours. A solution of 12.74 g (60.0 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture over 2 hours, adjusting the temperature to between -5 and 0 °C. The reaction mixture was reacted at 0°C for 1 hour, after which 70 g of ethanol was added and stirred at room temperature for 1 hour. The polyimide precursor was then precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure for 2 days. The weight-average molecular weight of this polyimide precursor (Polymer P-2) was 29,000. Polymer P-2 is a resin having the following structure: [ka]

[0353] <Synthesis Example 3: Synthesis of Polymer P-3> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with SOCl2, and a solution of 4,4'-diaminodiphenyl ether in N-methylpyrrolidone was added dropwise to the reaction mixture as in Synthesis Example 2. The resulting reaction mixture was then purified and dried. The weight-average molecular weight of this polyimide precursor (Polymer P-3) was 18,000. Polymer P-3 is a resin having the following structure: [ka]

[0354] The components were mixed as shown in Table 1 or Table 2 to prepare a uniform solution. The resulting solution was filtered under pressure at a pressure of 0.4 MPa through a filter with a pore width of 20 μm to obtain resin compositions (Compositions 1 to 20). Specifically, the content of each component shown in the table is the amount (parts by mass) shown in the table. In the table, "-" indicates that the composition does not contain the corresponding component.

[0355] [Table 1]

[0356] [Table 2]

[0357] Details of the abbreviations used in the table are as follows:

[0358] 〔resin〕 P-1 to P-3: Polymers P-1 to P-3 synthesized above

[0359] [Polymerizable compound] B-1: Tetraethylene glycol dimethacrylate (Arkema) B-2: OGSOL EA-0200 (Osaka Gas Chemicals Co., Ltd.) B-3: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

[0360] [Initiator] C-1: Irgacure OXE-01 (BASF) C-2: Parkmill D (NOF Corporation) C-3: Irgacure 784

[0361] [Metal adhesion improver] D-1: N-[3-(triethoxysilyl)propyl]maleamic acid D-2: X-12-1293 (Shin-Etsu Chemical Co., Ltd.) D-3: KR-513 (Shin-Etsu Chemical Co., Ltd.)

[0362] [Migration inhibitor] E-1: 5-aminotetrazole E-2 to E-5: Compounds of the following structure [ka]

[0363] [Polymerization inhibitor] A-1: 4MeHQ (4-methoxyphenol)

[0364] [Base Generator] G-1: The following compound [ka] G-2: The following compound [ka]

[0365] 〔solvent〕 H-1: GBL (γ-butyrolactone) H-2: DMSO (dimethyl sulfoxide) H-3: γ-valerolactone H-4: 3-Methoxy-N,N-dimethylpropanamide

[0366] [Filler] F-1: Boron nitride / 3M Platelets 001 (average particle size: 500 nm) F-2: Alumina / Sumitomo Chemical Co., Ltd., Sumicorundum AA-03NF (average particle size: 250 nm) F-3: Alumina / Sumitomo Chemical, NXA-150 (average particle size: 150 nm) F-4: Alumina / Sumitomo Chemical, NXA-100 (average particle size: 100 nm)

[0367] <Preparation of substrate> Pillar substrates with the following sizes and metal types were produced by plating. a) Pitch: 45 μm, copper pillar diameter: 10 μm, copper pillar height: 10 μm b) Pitch: 45 μm, copper / tin pillar diameter: 20 μm, copper / tin pillar height: 2 / 8 μm, silicon wafer, copper, and tin formed in this order. c) A 5 μm thick SiO2 film was formed on an 8-inch silicon wafer using CVD (chemical vapor deposition), and a square-array hole pattern with a pitch of 45 μm and a diameter of 20 μm was formed using photolithography and dry etching. Thin layers of titanium and copper were then formed in that order on the surface with the hole pattern using CVD, and the hole pattern was then filled with copper by plating. The SiO2 film with the copper-filled pattern, along with the copper inside, was then polished using CMP to a thickness of 3 μm.

[0368] The pillar substrate thus fabricated will be described in detail below. FIG. 6(a) is a schematic cross-sectional view of the above a). In FIG. 6(a), 10 denotes a substrate, and 12 denotes wiring terminals (pillars) formed of copper. In FIG. 6(a), the arithmetic mean value of the diameter d of each pillar is the pillar diameter, which is 10 μm in a). In FIG. 6(a), the arithmetic mean value of the spacing p between pillars in each pillar is the pitch, which is 45 μm in a). In FIG. 6(a), the arithmetic mean value of the height h of each pillar is the pillar height, which is 10 μm in a). FIG. 6(b) is a schematic cross-sectional view of the above b). In FIG. 6(b), 10 denotes a substrate and 12 denotes a wiring terminal, and the wiring terminal 12 is formed from a pillar (conductive path) 14 made of tin and a pillar (electrode) 16 made of copper. In FIG. 6(b), the arithmetic mean value of the pillar diameter d for each pillar is the pillar diameter, which is 20 μm in b). In FIG. 6(b), the arithmetic mean value of the spacing p between pillars in each pillar is the pitch, which is 45 μm in b). In FIG. 6(b), the arithmetic mean value of the height h1 of the conductive path in each pillar is the tin pillar height, which is 8 μm in b). In FIG. 6(b), the arithmetic mean value of the electrode height h2 in each pillar is the copper pillar height, which is 2 μm in b).

[0369] <Production of Substrate / Substrate Laminate (Joint) (Examples 1 to 11, 15 to 19, Comparative Examples 1 and 2)> In Examples 1 to 11 and 15 to 19, each composition listed in the table was applied to Substrates A and B to a thickness of 15 μm, followed by baking at 100°C for 5 minutes. Further baking was performed at the temperature and time conditions listed in the "Film Formation Temperature" and "Film Formation Time" columns in the table to obtain a polyimide-containing precursor part. The surface of the polyimide-containing precursor part was then planarized using a CMP (Chemical Mechanical Polishing) tool manufactured by Fujikoshi Machinery Co., Ltd., to leave a 5 μm residual film. The resulting chips were then cut into 5 mm squares using a dicing machine, and bonded using a flip-chip bonder manufactured by Toray Engineering Co., Ltd. under the conditions listed in the "Bonding Temperature," "Bonding Time," and "Pressure Force" columns in the table. The maximum peel resistance was then measured. In these examples, a chip on substrate A is bonded to a chip on substrate B, so the "Bonding" column in the table reads "chip-chip."

[0370] <Preparation of Substrate / Substrate Laminate (Joint) (Examples 12 and 13)> In Examples 12 and 13, Composition 6 was applied to Substrate A to a thickness of 15 μm and baked at 100°C for 5 minutes. Further baking was performed at the temperature and time conditions listed in the "Film Formation Temperature" and "Film Formation Time" columns in the table to obtain a polyimide-containing precursor part. The surface of the polyimide-containing precursor part was then planarized using a CMP (Chemical Polishing Machine) manufactured by Fujikoshi Machinery Co., Ltd., so that the remaining film thickness was 5 μm. The surface on the side of the polyimide-containing precursor part was then attached to dicing tape, polished with a polishing machine so that the remaining film thickness on the silicon substrate was 50 μm, and then cut into 5 mm squares using a dicing machine. Then, using a flip chip bonder manufactured by Toray Engineering Co., Ltd., three substrates were bonded in Example 12, and six substrates were bonded in Example 13. The bonding conditions were as listed in the "Bonding Temperature," "Bonding Time," and "Pressure Force" columns in the table. The maximum peel resistance was then measured. In these examples, three or six chips, which are substrate A, are bonded together, so the "Bonding" column in the table is written as "Chip-chip x 3" or "Chip-chip x 6."

[0371] <Production of Substrate / Substrate Laminate (Joint) (Example 14)> In Example 14, each composition listed in the table was applied to Substrate A and Substrate B listed in the table to a film thickness of 15 μm and baked at 100°C for 5 minutes. Further baking was performed at the temperature and time conditions listed in the "Film Formation Temperature" and "Film Formation Time" columns in the table to obtain a polyimide-containing precursor portion. The surface of the polyimide-containing portion was then planarized using a Fujikoshi Machinery Co., Ltd. CMP to leave a residual film of 5 μm. The polyimide surfaces of Substrate B and Substrate A were then bonded together using an EVG Bonder 540. The bonding conditions were as listed in the "Bonding Temperature," "Bonding Time," and "Pressure Force" columns in the table. After bonding, the substrates were cut into 5 mm squares using a dicing machine, and the maximum peel resistance was measured. In this example, a wafer (Substrate A) serving as Substrate A and a wafer (Substrate C) serving as Substrate B were bonded, so the "Bonding" column in the table reads "Wafer-Wafer."

[0372] <Preparation of Substrate / Substrate Laminate (Joint) (Examples 20 to 22)> In Example 20, each composition shown in the table was applied to Substrate A and Substrate B shown in the table to a film thickness of 7.5 μm, and baked at 100° C. for 5 minutes. Further, an i-line stepper exposure system FPA-3000i5+ (Canon Corporation) was used to apply 400 mJ / cm 2 The entire surface was exposed to an exposure amount of 1000 ppm. The film was then additionally baked under the temperature and time conditions described in the "Film Formation Temperature" and "Film Formation Time" columns to obtain a first layer of polyimide-containing precursor part. Furthermore, the above process from coating to additional baking was repeated on the first layer of polyimide-containing precursor part to perform a second layer coating. Thereafter, the same treatment as in Example 19 was carried out. Examples 21 and 22 were also treated in the same manner as above.

[0373] <Preparation of Substrate / Substrate Laminate (Joint) (Examples 23 and 24)> In Examples 23 and 24, each composition listed in the table was applied to Substrate A in a thickness of 15 μm and baked at 100°C for 5 minutes. Further baking was performed at the temperature and time conditions listed in the "Film Formation Temperature" and "Film Formation Time" columns in the table to obtain a polyimide-containing precursor portion. The surface of the polyimide-containing portion was then planarized using a CMP manufactured by Fujikoshi Machinery Co., Ltd. to leave a 5 μm residual film. The resulting substrate was then cut into 5 mm square chips using a dicing machine. These were then bonded using a flip-chip bonder manufactured by Toray Engineering Co., Ltd. under the conditions listed in the "Bonding Temperature," "Bonding Time," and "Pressure Force" columns in the table. The maximum peel resistance was then measured. In this example, a chip (substrate a) that is substrate A and a chip (substrate c) that is substrate B are bonded together, so the "bonding" column in the table is entered as "chip-chip."

[0374] <Preparation of Substrate / Substrate Laminate (Joint) (Examples 25 and 26)> <TEG(Test Element Group)チップ> A TEG wafer and an interposer wafer with Cu wiring under the pillars of the pillar substrate were prepared. These wafers contained a daisy chain pattern for measuring the conduction resistance. The TEG wafer pitch is 7 μm, the copper / tin pillar diameter is 3.5 μm, the copper / tin pillar height is 1 / 3 μm, and the silicon wafer, SiO2, copper, and tin are formed in this order. The interposer includes wiring around the periphery, so the chip size is 10mm square. The interposer pitch is 7 μm, the copper pillar diameter is 4 μm, the silicon wafer, SiO2, and copper are formed in this order. The interposer did not have tin pillars formed, and was planarized using a CMP manufactured by Fujikoshi Machinery Co., Ltd. so that the copper and SiO2 were on the same plane. In Examples 25 and 26, each composition listed in the table was applied to Substrate A (TEG wafer) to a thickness of 15 μm and baked at 100°C for 5 minutes. Further baking was performed at the temperature and time conditions listed in the "Film Formation Temperature" and "Film Formation Time" columns in the table to obtain a polyimide-containing precursor portion. The surface of the polyimide-containing portion was then planarized using a CMP manufactured by Fujikoshi Machinery Co., Ltd., so that the remaining film thickness was 3 μm. Substrate A was then cut into 5 mm square pieces and Substrate B into 10 mm square pieces using a dicing machine to create chips, and these were then bonded using a flip-chip bonder manufactured by Toray Engineering Co., Ltd. under the conditions listed in the "Bonding Temperature," "Bonding Time," and "Pressure Force" columns in the table. 7 and 8 are schematic cross-sectional views showing the details of the operations carried out in Examples 25 and 26 above. 7(a) is a schematic cross-sectional view of substrate A (TEG wafer) 60. Substrate A 60 includes an SiO2 layer 62 and electrodes (daisy chain pattern) 63 on a silicon wafer 61. The electrodes 63 are formed of Cu wiring 63a and tin pillars 63b formed on the exposed portions of the Cu wiring 63a from the SiO2 layer 62. The pitch, copper / tin pillar diameter, and copper / tin pillar height in the TEG wafer are as described above. FIG. 7(b) shows the state in which the polyimide-containing precursor portion 64 was formed using the composition shown in the table and then planarized. Fig. 7(c) is a schematic cross-sectional view of a chip 65 having a width W1 of 5 mm, which is obtained by cutting the substrate A60 shown in Fig. 7(b) using the dicing machine. 8(a) is a schematic cross-sectional view of substrate B (interposer wafer) 70. Substrate B 70 includes an SiO2 layer 72 and electrodes (daisy chain pattern) 73 on a silicon wafer 71. The electrodes 73 are made of copper, and the pitch and copper pillar diameter in the interposer wafer are as described above. Fig. 8(b) shows a chip 74 having a width W2 of 10 mm, which is obtained by cutting the substrate B70 shown in Fig. 8(a) with the dicing machine. 8(c) shows the state in which chip 65 and chip 74 are joined by the above-mentioned method. Here, by checking the electrical resistance between terminal a and terminal b of electrode 73, it can be determined whether the circuit formed by electrode 63 and electrode 73 is conductive. In this example, the chip (TEG chip) on substrate A is bonded to the chip (interposer chip) on substrate B, so the "Bonding" column in the table reads "chip-chip."

[0375] <Preparation of Substrate / Substrate Laminate (Joint) (Examples 27 to 31)> In Examples 27 to 31, each composition listed in the table was applied to Substrate A to a thickness of 15 μm and baked at 100°C for 5 minutes. Further baking was performed at the temperature and time conditions listed in the "Film Formation Temperature" and "Film Formation Time" columns in the table to obtain a polyimide-containing precursor portion. The surface of the polyimide-containing portion was then planarized using a CMP (Fujikoshi Machinery Co., Ltd.) to leave a 5 μm residual film. The substrate was then cut into 5 mm squares using a dicing machine to create chips, which were then bonded using a flip-chip bonder (Toray Engineering Co., Ltd.) under the conditions listed in the "Bonding Temperature," "Bonding Time," and "Pressure" columns in the table. Each resulting substrate laminate was then heat-treated in an oven under the conditions listed in the "Annealing Temperature," "Annealing Time," and "Annealing Atmosphere" columns in the table. The maximum peel resistance was then measured. In these examples, Substrate A (chip a)) and Substrate B (chip b)) were bonded, so the "Bonding" column in the table reads "Chip-Chip." The maximum peel resistance was measured in the same manner as described in "Evaluation of maximum peel resistance" below, and the evaluation results are shown in the "Maximum peel resistance after annealing" column in the table. The evaluation criteria were as follows: The greater the maximum peel resistance, the better the adhesiveness of the bonded body. The cyclization rate of the polyimide in the polyimide-containing portion after the annealing step was measured by the same method as in the "cyclization rate after joining" described later, and is shown in the "cyclization rate after annealing" column in the table. The unit of the values ​​is "%." -Evaluation criteria- S: Maximum peel resistance is 400 kg / cm 2 That was all. A: Maximum peel resistance is 100kg / cm 2 More than 400kg / cm 2 It was less than. B: Maximum peel resistance is 100 kg / cm 2 Less than 70kg / cm 2 That was all. C: Maximum peel resistance is 70 kg / cm 2 Less than 40kg / cm 2 That was all. D: Maximum peel resistance is 40 kg / cm 2 It was less than.

[0376] <Evaluation of maximum peel resistance> Each of the obtained substrate laminates was cut into a size of 5 mm x 5 mm using a dicing machine, and the maximum peel resistance (kg / cm) of a 7 mm x 7 mm size was measured using a Condor Sigma die tester manufactured by XYZTEC. 2 ) was measured. Five test pieces were prepared for each level, and measurements were taken five times for each level, with the arithmetic mean value being used. The maximum peel resistance was evaluated using the following four levels. The evaluation results are shown in the "Maximum peel resistance" column in the table. The higher the maximum peel resistance, the better the adhesiveness of the bonded structure. A: Maximum peel resistance is 100kg / cm 2 That was all. B: Maximum peel resistance is 100 kg / cm 2 Less than 70kg / cm 2 That was all. C: Maximum peel resistance is 70 kg / cm 2 Less than 40kg / cm 2 That was all. D: Maximum peel resistance is 40 kg / cm 2 It was less than.

[0377] <Measurement of cyclization rate> The cyclization rates of the polyimide in the polyimide-containing precursor part formed on the substrate A and the second polyimide-containing precursor part formed on the substrate B were measured by the above-mentioned measurement method, and are each shown in the column "Cyclization rate before joining" in the table. The cyclization rate of the polyimide in the polyimide-containing portion after bonding was measured by the above-mentioned method and is shown in the column "Cyclization rate afte...

Claims

1. A step of preparing a substrate A having a surface provided with wiring terminals; a polyimide-containing precursor portion forming step of applying a polyimide-containing precursor portion forming composition to the surface of the substrate A that includes the wiring terminals, and forming a polyimide-containing precursor portion on the surface of the substrate A that includes the wiring terminals; preparing a substrate B having a surface with wiring terminals; a bonding step of bonding a surface of the substrate A having a polyimide-containing precursor portion to a surface of the substrate B having the wiring terminals; Including, a difference between a cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; The polyimide-containing precursor portion-forming composition contains a polyimide precursor and a solvent, and the polyimide precursor contains a repeating unit represented by the following formula (2): A method for manufacturing a bonded body. 【Chemistry 1】 In formula (2), A 1 and A 2 each independently represent an oxygen atom or —NH—, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 contains a polymerizable group.

2. A process of preparing a substrate A having a surface with wiring terminals; a polyimide-containing precursor portion forming step of forming a polyimide-containing precursor portion on the surface of the substrate A that includes the wiring terminals; preparing a substrate B having a surface with wiring terminals; a bonding step of bonding a surface of the substrate A having a polyimide-containing precursor portion to a surface of the substrate B having the wiring terminals; Including, a difference between a cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; The bonding temperature in the bonding step is equal to or higher than the melting point of the wiring terminal of the substrate A. A method for manufacturing a bonded body.

3. 3. The method for producing a bonded body according to claim 1, wherein the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step is 40 to 90%.

4. 3. The method for producing a bonded body according to claim 1, wherein a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 91 to 100%.

5. The method for manufacturing a bonded body according to claim 1 or 2, wherein the bonding temperature in the bonding step is 380° C. or less.

6. 3. The method for manufacturing a bonded body according to claim 1, wherein the bonding temperature in the bonding step is equal to or higher than the melting point of the wiring terminal of the substrate A and equal to or higher than the melting point of the wiring terminal of the substrate B.

7. The polyimide-containing precursor part forming step includes: The method for producing a bonded body according to claim 1 , further comprising heating the applied polyimide-containing precursor portion-forming composition at a temperature lower than the melting point of the wiring terminal of the substrate A.

8. The method for producing a bonded body according to claim 1 or 2, wherein the substrate A is in the form of a wafer.

9. The method for producing a bonded structure according to claim 1 or 2, wherein the substrate B is in the form of a chip.

10. The method for producing a bonded body according to claim 1 or 2, wherein the substrate B is in the form of a wafer.

11. The method further includes a planarization step of planarizing the surface of the polyimide-containing precursor portion of the substrate A, The method for producing a bonded body according to claim 1 or 2, comprising the polyimide-containing precursor portion forming step, the planarizing step, and the bonding step in this order.

12. 3. The method for producing a bonded body according to claim 1, wherein in the bonding step, an electrode included in a surface of the substrate A having the polyimide-containing precursor portion and an electrode on a surface of the substrate B having the wiring terminal are bonded so as to be in direct contact with each other.

13. a second polyimide-containing precursor portion forming step of forming a second polyimide-containing precursor portion on the surface of the substrate B that includes the wiring terminals, The method for producing a bonded body according to claim 1 or 2, comprising the second polyimide-containing precursor portion forming step and the bonding step in this order.

14. 14. The method for producing a joined body according to claim 13, wherein a difference between a cyclization rate of the polyimide in the second polyimide-containing precursor portion before the joining step and a cyclization rate of the polyimide contained in the polyimide-containing portion formed at the joined portion after the joining step is 5% or more.

15. 14. The method for producing a bonded body according to claim 13, wherein a cyclization rate of the polyimide in the second polyimide-containing precursor portion before the bonding step is 40 to 90%.

16. The method for manufacturing a bonded body according to claim 1 or 2, wherein the substrate B includes an inorganic insulating film between the wiring terminals of the substrate B.

17. the polyimide-containing precursor part forming step is a step of applying a polyimide-containing precursor part forming composition onto the surface of the substrate A that includes the wiring terminals, The method for producing a bonded body according to claim 2 , wherein the polyimide-containing precursor portion-forming composition contains a polyimide precursor and a solvent.

18. The method for producing a bonded body according to claim 1 or 17, wherein the polyimide-containing precursor portion-forming composition contains a migration inhibitor.

19. The method for producing a bonded body according to claim 1 , wherein the polyimide-containing precursor portion-forming composition contains a polymerizable compound having a ring structure.

20. 18. The method for producing a bonded body according to claim 1, wherein the polyimide-containing precursor portion-forming composition contains a polymerizable compound whose homopolymer has a glass transition temperature of 200°C or higher.

21. The method for producing a bonded body according to claim 1 or 17, wherein the polyimide-containing precursor portion-forming composition contains a filler.

22. A step of preparing a substrate C having two or more surfaces provided with wiring terminals; A step of preparing a plurality of substrates D each having a surface provided with wiring terminals; a polyimide-containing precursor portion forming step of applying a polyimide-containing precursor portion forming composition to a surface of at least one of the substrates C and D, the surface including the wiring terminals, to form a polyimide-containing precursor portion; and a bonding step of bonding a surface of the substrate D having the wiring terminals to each of at least two of the surfaces of the substrate C having the wiring terminals; Including, each of the plurality of bonding portions in the bonding step includes the polyimide-containing precursor portion; in at least one bonded portion, a difference between a cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; The polyimide-containing precursor portion-forming composition contains a polyimide precursor and a solvent, and the polyimide precursor contains a repeating unit represented by the following formula (2): A method for manufacturing a laminate. 【Chemistry 2】 In formula (2), A 1 and A 2 each independently represent an oxygen atom or —NH—, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 contains a polymerizable group.

23. A step of preparing a substrate C having two or more surfaces equipped with wiring terminals; A step of preparing a plurality of substrates D each having a surface provided with wiring terminals; a polyimide-containing precursor portion forming step of forming a polyimide-containing precursor portion on a surface of at least one of the substrates C and D that includes the wiring terminals; and a bonding step of bonding a surface of the substrate D having the wiring terminals to each of at least two of the surfaces of the substrate C having the wiring terminals; Including, each of the plurality of bonding portions in the bonding step includes the polyimide-containing precursor portion; in at least one bonded portion, a difference between a cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; The bonding temperature in the bonding step is equal to or higher than the melting point of the wiring terminal of the substrate C. A method for manufacturing a laminate.

24. The method for producing a laminate according to claim 22 or 23, wherein the polyimide-containing precursor portion contains a filler.

25. A method for manufacturing a device, comprising the method for manufacturing a bonded structure according to claim 1 or 2.

26. A step of preparing a substrate A having a surface provided with wiring terminals; a polyimide-containing precursor portion forming step of applying a polyimide-containing precursor portion forming composition to the surface of the substrate A that includes the wiring terminals, and forming a polyimide-containing precursor portion on the surface of the substrate A that includes the wiring terminals; preparing a substrate B having a surface with wiring terminals; a bonding step of bonding a surface of the substrate A having a polyimide-containing precursor portion to a surface of the substrate B having the wiring terminals; A polyimide-containing precursor portion-forming composition used in a method for producing a bonded body, comprising: the polyimide-containing precursor part is a member formed from the polyimide-containing precursor part-forming composition, a difference between a cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; The polyimide-containing precursor portion-forming composition contains a polyimide precursor and a solvent, and the polyimide precursor contains a repeating unit represented by the following formula (2): A polyimide-containing precursor portion-forming composition. 【Transformation 3】 In formula (2), A 1 and A 2 each independently represent an oxygen atom or —NH—, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 contains a polymerizable group.

27. ​​A step of preparing a substrate A having a surface with wiring terminals; a polyimide-containing precursor portion forming step of forming a polyimide-containing precursor portion on the surface of the substrate A that includes the wiring terminals; preparing a substrate B having a surface with wiring terminals; a bonding step of bonding a surface of the substrate A having a polyimide-containing precursor portion to a surface of the substrate B having the wiring terminals; A polyimide-containing precursor portion-forming composition used in a method for producing a bonded body, comprising: the polyimide-containing precursor part is a member formed from the polyimide-containing precursor part-forming composition, a difference between a cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and a cyclization rate of polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 5% or more; The bonding temperature in the bonding step is equal to or higher than the melting point of the wiring terminal of the substrate A. A polyimide-containing precursor portion-forming composition.

28. The polyimide-containing precursor part forming composition according to claim 26 or 27, wherein a cyclization rate of the polyimide in the polyimide-containing precursor part before the bonding step is 40 to 90%.

29. 28. The polyimide-containing precursor portion-forming composition according to claim 26, wherein a cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is 91 to 100%.

30. The polyimide-containing precursor part-forming composition according to claim 26 or 27, further comprising a filler.

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