Composition for forming a polyimide-containing portion, method for manufacturing a joint, joint, method for manufacturing a device, and device.

Abstract

Provided is a composition for forming a polyimide-containing part, the composition being used in a joined body manufacturing method including: a step of preparing a substrate A; a polyimide-containing part forming step of forming a polyimide-containing part on the surface of the substrate A on which wiring terminals are provided; a step of preparing a substrate B; a joining step of joining the surface having the polyimide-containing part of the substrate A and the surface of the substrate B on which wiring terminals are provided. The polyimide-containing part is a member formed from the composition for forming a polyimide-containing part. The glass transition temperature of the polyimide-containing part is lower than the joining temperature of the joining step. Also provided are a joined body manufacturing method using the composition for forming a polyimide-containing part, a joined body, a device manufacturing method, and a device.

Description

[Technical Field]

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

[0002] Electronic devices such as mobile phones and tablet terminals are becoming increasingly smaller, while their functions are becoming more diverse. To meet these needs, the electronic circuits incorporated into these devices require further miniaturization, high integration, and high-density mounting. 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 multi-functionality, high performance, and reliability. These technologies are expected to reduce the cost of electronic devices because they reduce the number of components and simplify the semiconductor manufacturing process.

[0003] However, because SIPs connect chips using wire bonding, it is difficult to achieve processing speeds equivalent to conventional SOCs (System on Chip). Furthermore, wire bonding cumbersome manufacturing processes, and improvements in product cost and quality were desired. To address these challenges, COC (Chip on Chip) mounting technology was developed. COCs connect chips using flip-chip connections, shortening the transmission distance and enabling high-speed performance equivalent to SOCs. Figure 1 is a cross-sectional view showing the structure of a typical COC. In this example, the COC comprises a daughter chip (first substrate) 1 and a mother chip (second substrate) 2. Electronic circuits (not shown) and flip-chip electrodes (not shown) are formed on the mother chip 2, and the daughter chip 1 is supported and connected via solder electrodes (bumps) 93. The area around the solder electrodes 93 is filled with underfill 94 to ensure insulation. The mother chip 2 is mounted on a base substrate 98 by bonding film 91, maintaining insulation. The electrical connection is made via wire bonding pads 97b, wire bonding 96, and substrate electrodes 97a. This 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 electronic equipment via these. Furthermore, techniques and materials for three-dimensional packaging using TSV (Through Silicon Via) are being investigated as a further application of this flip-chip packaging technology (Non-Patent Literature 1). [Prior art documents] [Non-patent literature]

[0004] [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 [Overview of the project] [Problems that the invention aims to solve]

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

[0006] Therefore, the present invention aims to provide a polyimide-containing portion forming composition that yields a bonded body with a high maximum peel resistance between two substrates when two substrates are joined, a method for manufacturing a bonded body using the polyimide-containing portion forming composition, a bonded body obtained by the manufacturing method, a method for manufacturing a device including the method for manufacturing the bonded body, and a device including the bonded body. [Means for solving the problem]

[0007] Examples of specific embodiments of the present invention are shown below. <1> A step of preparing a substrate A having a surface equipped with wiring terminals, A polyimide-containing portion forming step, in which a polyimide-containing portion is formed on the surface of the substrate A that has the above wiring terminals, A step of preparing a substrate B having a surface equipped with wiring terminals, and A polyimide-containing portion forming composition used in a method for manufacturing a bonded body, which includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion to the surface of the substrate B having the wiring terminals, The above polyimide-containing portion is a component formed from the above polyimide-containing portion forming composition, The glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding process. Composition for forming polyimide-containing parts. <2> A polyimide precursor and a solvent are included. <1> The composition for forming the polyimide-containing portion described above. <3> Further containing a migration inhibitor, <1> or <2> The composition for forming the polyimide-containing portion described above. <4> The glass transition temperature of the polyimide-containing portion is 350°C or lower. <1> ~ <3> A composition for forming a polyimide-containing portion as described in any one of the following. <5> The glass transition temperature of the polyimide-containing portion is 30°C or more lower than the bonding temperature in the bonding process. <1> ~ <4> A composition for forming a polyimide-containing portion as described in any one of the following. <6> The bonding temperature in the above bonding process is 380°C or lower. <1> ~ <5> A composition for forming a polyimide-containing portion as described in any one of the following. <7> The form of the substrate A described above is a wafer. <1> ~ <6> A composition for forming a polyimide-containing portion as described in any one of the following. <8> The form of the above substrate B is a chip. <1> ~ <7> A composition for forming a polyimide-containing portion as described in any one of the following. <9> The form of the substrate B described above is a wafer. <1> ~ <7> A composition for forming a polyimide-containing portion as described in any one of the following. <10> In the bonding process, the temperature of substrate A, which contains polyimide, is preheated to 70°C or higher. <1> ~ <9> A composition for forming a polyimide-containing portion as described in any one of the following. <11> Between the above polyimide-containing portion formation step and the above bonding step, a planarization step is included to planarize the surface of the polyimide-containing portion of the substrate A. <1> ~ <10> A composition for forming a polyimide-containing portion as described in any one of the following. <12> The above planarization process is performed by physical polishing. <11> The composition for forming the polyimide-containing portion described above. <13> The above planarization process is carried out by chemical polishing. <11> The composition for forming the polyimide-containing portion described above. <14> In the above bonding process, the electrodes included in the surface of substrate A having a polyimide-containing portion and the electrodes on the surface of substrate B having the wiring terminals are bonded together in direct contact. <1> ~ <13> A composition for forming a polyimide-containing portion as described in any one of the following. <15> Prior to the bonding step, the process further includes a second polyimide-containing portion formation step in which a second polyimide-containing portion is formed on the surface of the substrate B that has the wiring terminals. <1> ~ <14> A composition for forming a polyimide-containing portion as described in any one of the following. <16> Further comprising a photosensitive compound, <1> ~ <15> A composition for forming a polyimide-containing portion as described in any one of the following. <17> The above polyimide-containing portion formation step includes applying the polyimide-containing portion formation composition to the surface of the substrate A having the above wiring terminals and heating it. <1> ~ <16> A composition for forming a polyimide-containing portion as described in any one of the following. <18> The heating temperature in the above heating process is 375°C or lower. <17> The composition for forming the polyimide-containing portion described above. <19> A step of preparing a substrate A having a surface equipped with wiring terminals, A polyimide-containing portion forming step, in which a polyimide-containing portion is formed on the surface of the substrate A that has the above wiring terminals, A step of preparing a substrate B having a surface equipped with wiring terminals, and The process includes a bonding step of joining the surface of substrate A having a polyimide-containing portion to the surface of substrate B having the wiring terminals, A method for manufacturing a bonded body, wherein the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding process. <20> <19> A joint obtained by the manufacturing method described above. <21> <19> A method for manufacturing a device, including a method for manufacturing a joint described above. <22> <20> A device including the joint described above. [Effects of the Invention]

[0008] The present invention provides a polyimide-containing portion forming composition that yields a bonded body with a high maximum peel resistance between two substrates when two substrates are joined, a method for manufacturing a bonded body using the polyimide-containing portion forming composition, a bonded body obtained by the manufacturing method, a method for manufacturing a device including the method for manufacturing the bonded body, and a device including the bonded body. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing the structure of a COC semiconductor device. [Figure 2] This is a schematic cross-sectional diagram illustrating the steps involved in joining substrates using a method for manufacturing a bonded body in which the polyimide-containing composition for forming a part of the present invention, according to one embodiment of the present invention, is used. [Figure 3] This is a schematic cross-sectional diagram illustrating the steps involved in joining substrates using a method for manufacturing a bonded body in which the polyimide-containing composition for forming a part of the present invention, according to one embodiment of the present invention, is used (continuation of Figure 2). [Figure 4] This is a schematic cross-sectional diagram illustrating the steps involved in joining a substrate using a method for manufacturing a bonded body in which the polyimide-containing composition for forming a part of the present invention, according to one embodiment of the present invention, is used (continuation of Figure 3). [Figure 5] This is a schematic cross-sectional view showing an example of a three-dimensionally packaged semiconductor device using TSV. [Figure 6] This is a schematic cross-sectional view showing details of the substrate used in the embodiment. [Modes for carrying out the invention]

[0010] The details of 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 this specification, when groups (atomic groups) are not explicitly labeled as substituted or unsubstituted, the term includes both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also 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. Generally, the light used for exposure includes the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, "(meth)acrylate" refers to both "acrylate" and "methacrylate," or either of them; "(meth)acrylic" refers to both "acrylic" and "methacrylic," or either of them; and "(meth)acryloyl" refers to both "acryloyl" and "methacryloyl," or either of them. In this specification, the term "process" includes not only independent processes but also any process that is not clearly distinguishable from other processes, as long as its intended function is achieved. In this specification, solids content refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. Furthermore, unless otherwise specified, the solids content concentration refers to the concentration at 25°C. In this invention, the temperature is 25°C unless otherwise specified. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values ​​according to gel permeation chromatography (GPC measurement), unless otherwise specified. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and one of the following columns: Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluent shall be THF (tetrahydrofuran). Unless otherwise specified, detection shall be performed using a UV (ultraviolet) wavelength 254 nm detector.

[0011] (Composition for forming polyimide-containing parts) The polyimide-containing portion forming composition of the present invention is used in a method for manufacturing a bonded body, which includes the steps of: preparing a substrate A having a surface with wiring terminals; forming a polyimide-containing portion on the surface of the substrate A having the wiring terminals; preparing a substrate B having a surface with wiring terminals; and joining the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminals, wherein the polyimide-containing portion is a member formed from the polyimide-containing portion forming composition, and the glass transition temperature of the polyimide-containing portion is lower than the joining temperature in the joining step.

[0012] By using the polyimide-containing portion forming composition of the present invention (hereinafter also simply referred to as "resin composition"), it becomes possible to manufacture a bonded body with a high maximum peel resistance between two substrates when joining two substrates, such as wafer to wafer or wafer to chip, via a polyimide-containing portion. Specifically, by adopting a configuration in which the glass transition temperature (Tg) of the polyimide-containing portion is lower than the bonding temperature, sufficient fluidity of the polyimide-containing portion can be ensured during bonding, thereby increasing the maximum peel resistance during bonding. In this invention, the bonding temperature is the temperature of the polyimide-containing portion at the time of bonding, and can be, for example, the set temperature of the equipment used for bonding.

[0013] Furthermore, by using a higher temperature during bonding, the bonding time can be shortened, thereby reducing the cycle time of the bonding process. When joining two substrates as described above, if the alignment accuracy during joining is low, misalignment may occur between metal parts such as electrodes on each substrate, resulting in exposed wiring sections. In such cases, the polyimide-containing sections between the wiring sections require high voltage resistance. Here, for example, if a migration inhibitor is included in the composition for forming the polyimide-containing portion, it is possible to suppress the migration of metal from the metal portion to the polyimide-containing portion, thereby improving the dielectric strength. The resin composition of the present invention will be described in detail below.

[0014] <Preparation of substrate A> A method for manufacturing a bonded body using the polyimide-containing composition of the present invention includes the step of preparing a substrate A having a surface equipped with wiring terminals. In the preparation process, substrate A may be manufactured by known methods (for example, plating on a substrate such as a silicon substrate) or obtained by means of purchase or other means.

[0015] [Substrate A] Substrate A has a side with wiring terminals. Hereafter, the wiring terminals on circuit board A will also be referred to as wiring terminal A.

[0016] The substrate A may be a wafer or a chip, but being a wafer is also one of the preferred embodiments of the present invention. In this invention, a wafer refers to a substrate containing a semiconductor, and is a concept that includes panels formed from multiple semiconductor elements. In the present invention, a chip refers to a semiconductor-containing individual piece formed by dicing or the like, and may be a single-sided chip or a double-sided chip.

[0017] The shape of substrate A is not particularly limited, but examples include a polygonal flat plate, a disc, or a polyhedron. The thickness of substrate A is preferably 0.1 to 5 mm, and more preferably 0.2 to 1 mm. The wiring terminal A on substrate A is preferably a pillar electrode. Furthermore, the above-mentioned 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 more preferably at least one metal selected from the group consisting of copper, tin, and nickel. In this specification, the term "containing metal X" is used to collectively refer to the presence of at least one of metal X or an alloy containing that metal. Note that the alloy may contain elements other than those exemplified above. For example, a copper alloy may contain silicon atoms to form a Colson alloy. In addition, oxygen which is inevitably dissolved, and organic residues of the raw material compounds which are mixed in during precipitation, may be present. The above-mentioned wiring terminal A may be a wiring terminal comprising multiple different components. For example, the substrate may have a portion (hereinafter also referred to as "electrode") made of a metal such as copper, silver, gold, or an alloy containing one or more of these, which is used as an electrode, and a portion (hereinafter also referred to as "conducting passage") made of a metal such as nickel, tin, lead, or an alloy containing one or more of these, which is used as solder, which is formed on the copper electrode, and the electrode and the conducting passage may be in series to form one wiring terminal A. Among these, it is preferable that the wiring terminal A comprises at least a copper-containing member and a tin-containing member. An example of a substrate A having a surface equipped with such a wiring terminal A is the substrate b) used in the embodiment of the present invention. In substrate b), a tin-based conductive passage is formed on an electrode made of copper.

[0018] Furthermore, the materials used for the electrodes are not particularly limited, but examples include tin, gold, silver, copper, aluminum, tungsten, palladium, platinum, cobalt, nickel, zinc, ruthenium, iridium, rhodium, or alloys thereof. Among these, metals containing copper, metals containing aluminum, metals containing tungsten, metals containing nickel, or metals containing gold are preferred as electrodes, metals containing copper are more preferred, and copper is even more preferred. It is preferable to use a metal that does not melt during the bonding process as the metal used for the electrodes. 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 for example, it is preferable to have a melting point of 3000°C or lower. The materials used for the conduit are not particularly limited, but include tin, lead, silver, copper, zinc, bismuth, or indium, or alloys thereof. In particular, in this invention, solder made of tin or tin alloy (metal containing tin) is preferred. Recently, lead-free soldering technology has also advanced, and it is also preferable to select such materials. The metal used for the conduit is preferably a metal that melts during the joining process. The melting point of the metal used for the conduit 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 if the metal is solid at room temperature, but it is preferably, for example, 150°C or higher. Furthermore, it is preferable that multiple wiring terminals A are formed on the substrate A.

[0019] The material used for substrate A is not particularly limited and can include semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, as well as quartz, glass, optical films, ceramic materials, vapor-deposited 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 layers such as an adhesion layer or oxide layer made of hexamethyldisilazane (HMDS) on its surface. In this invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates (silicon wafers) are more preferred. Substrate A may have an electronic circuit region including an electronic circuit. The electronic circuit may also have elements such as semiconductors. Furthermore, it is preferable that the electronic circuit is electrically connected to the wiring terminal A. When substrate A is a wafer, its size can be 100 mm or more in diameter (or maximum diameter if substrate A is not circular). For larger substrates, it is preferable that the size be 200 mm or more, and more preferably 250 mm or more. There is no particular upper limit, but it is preferable that the size be 2,000 mm or less. When substrate A is a chip, the size is preferably such that the diameter (or maximum diameter if substrate A is not circular) is 7 mm or more, more preferably 10 mm or more, and even more preferably 20 mm or more. As an upper limit, for example, it is preferably 50 mm or less, more preferably 40 mm or less, and even more preferably 30 mm or less.

[0020] <Polyimide-containing part formation process> A method for manufacturing a bonded body using the polyimide-containing composition of the present invention includes a polyimide-containing portion forming step in which a polyimide-containing portion is formed on the surface of the substrate A that has the wiring terminal (wiring terminal A). The polyimide-containing portion is preferably formed to be in contact with the wiring terminal A, and more preferably formed to fill the recess between the wiring terminals A. Furthermore, while the polyimide-containing portion only needs to be formed on at least a part of the wiring terminal A, for example, forming it on all of the wiring terminal A is also one of the preferred embodiments of the present invention. The above polyimide-containing portion formation step preferably includes applying the polyimide-containing portion formation composition to the surface of substrate A equipped with the wiring terminals and heating it. Details of the application and heating will be described later.

[0021] [Polyimide-containing portion] The polyimide-containing portion is a component formed from the polyimide-containing portion forming composition, and it is preferable that the component is obtained by at least heating the polyimide-containing portion forming composition.

[0022] The polyimide-containing portion is a component containing polyimide, and may further contain components other than polyimide. Other components besides polyimide include components other than polyimide and its precursors contained in the resin composition described later, and components that have been modified (decomposed, polymerized, structurally changed, etc.) by heating.

[0023] The glass transition temperature of the polyimide-containing portion should be lower than the bonding temperature in the bonding process, but it is preferably 350°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower. The lower limit of the glass transition temperature is not particularly limited, but from the viewpoint of heat resistance, it is preferably 200°C or higher. From the viewpoint of increasing the maximum peel resistance, the glass transition temperature of the polyimide-containing portion is preferably 30°C or more lower than the bonding temperature in the bonding process, more preferably 50°C or more lower, and even more preferably 70°C or more lower. Furthermore, it is preferable that the glass transition temperature of the polyimide-containing portion is 30°C or more higher than the bonding temperature in the bonding process.

[0024] The thickness of the polyimide-containing part is not particularly limited, but from the perspective of exerting the effects of its physical properties, it is preferably 100 nm or more, more preferably 300 nm or more, still more preferably 500 nm or more, even more preferably 1 μm or more, and even more preferably 2 μm or more in terms of the thickness immediately before the bonding step (when the planarization step described later is performed, the thickness in the state immediately before the planarization step). There is no particular upper limit, but it is preferably 1 mm or less, more preferably 500 μm or less, and still more preferably 200 μm or less. The film thickness can be measured using a known film thickness measuring device.

[0025] The thermal diffusivity of the polyimide-containing part in the bonded body described later is preferably 2.0×10 -7 m 2 s -1 or more, and more preferably 3.0×10 -7 m 2 s -1 or more, and still more preferably 5.0×10 -7 m 2 s -1 or more. The thermal diffusivity of the polyimide-containing part can be adjusted by design, for example, when the polyimide-containing part contains a filler, the type of filler material, the particle size of the filler (when two or more kinds of fillers are included, the combination of their particle sizes), the thermal diffusivity of the filler, the filler content, the structure of the polyimide, the thermal diffusivity of the polyimide, the polyimide content, etc.

[0026] The polyimide-containing part is preferably an insulating member. The insulation property (electrical resistance) of the polyimide-containing part is not particularly limited, but the volume resistivity is preferably 1×10 15 Ω·cm or more, and more preferably 1×10 16 Ω·cm or more. There is no particular upper limit, but it is preferably 1×10 19It is practical for the volume resistivity to be Ω·cm or less. The dielectric breakdown voltage is preferably 1kV / mm or more, and more preferably 10kV / mm or more. There is no particular upper limit, but it is practical for it to be 1000kV / mm or less. In this specification, the measurement of volume resistivity and dielectric breakdown voltage shall be in accordance with JIS C2151:2006 and JIS C2318:2007.

[0027] [Applicable process] The polyimide-containing portion formation step preferably includes an application step of the polyimide-containing portion formation composition (resin composition) of the present invention onto the surface of the substrate A having the wiring terminals A.

[0028] Examples of methods for applying the resin composition onto 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 film thickness, spin coating, slit coating, spray coating, or inkjet coating are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. 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. In the case of spin coating, for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm. Alternatively, a method can be applied in which a coating film, which has been formed in advance on a temporary support using the above application method, is transferred onto a substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Publication No. 2006-047592 can be suitably used in the present invention as well. Furthermore, a process to remove excess film from the edges of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing. Alternatively, a pre-wetting process may be employed in which the substrate is coated with various solvents to improve its wettability before applying the resin composition to the substrate.

[0029] Furthermore, if the resin composition contains a solvent, the process may include a drying step (a drying step) in which the component made of the resin composition (hereinafter also simply referred to as "film") is dried after the resin composition has been applied to the substrate A. The drying temperature in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0030] The thickness immediately after application (or the thickness after drying if a drying process is performed) is not particularly limited and should be adjusted as appropriate so that the thickness of the resulting polyimide-containing portion is as described below.

[0031] The polyimide-containing portion formation step may include a step of patterning a component made of a resin composition. If a resin composition containing a photosensitive compound such as a photopolymerization initiator, as described later, is used, this patterning can be carried out by exposure and development. After the polyimide-containing portion is formed, its surface may be planarized. Details of the planarization will be described later. If patterning is performed, the thickness of the portion removed by development, etc., will not be used in the calculation of the film thickness difference (T1-T2) described later.

[0032] [Exposure process] The above film may be subjected to an exposure process in which the film is selectively exposed. In other words, the method for producing the polyimide-containing portion (hereinafter also referred to as "cured product") according to the polyimide-containing portion forming composition of the present invention may include an exposure step of selectively exposing the film formed by the application step. Selective exposure means exposing only a portion of a film. Selective exposure creates areas on the film that are exposed (exposed regions) and areas that are not exposed (unexposed regions). The exposure amount is not particularly defined as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm² in terms of exposure energy at a wavelength of 365 nm. 2 Preferably, 200-8,000 mJ / cm² 2 This is preferable.

[0033] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0034] In relation to the light source, the exposure wavelengths include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (g, h, i-line wavelengths), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic 532nm and third harmonic 355nm of YAG lasers. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and among these, exposure with the i-line is preferred. This can result in particularly high exposure sensitivity. Furthermore, the exposure method is not particularly limited, and any method in which at least a portion of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0035] <Post-exposure heating process> The above film may be subjected to a heating step after exposure (post-exposure heating step). In other words, the method for producing a cured product according to the polyimide-containing composition of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating process is preferably 1 to 12°C / min from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. Furthermore, the heating rate may be changed as needed during the heating process. The heating means in the post-exposure heating process is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0036] <Developing process> The film after exposure may be subjected to a developing process in which it is developed using a developing solution to form a pattern. In other words, the method for producing a cured product according to the polyimide-containing composition of the present invention may include a developing step in which a film exposed in an exposure step is developed using a developer to form a pattern. By performing the developing step, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed parts of the film are removed by the development process is called negative development, and development in which the exposed parts of the film are removed by the development process is called positive development.

[0037] [Developer] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0038] When the developing solution is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, 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 are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, when using TMAH, for example.

[0039] If the developer contains an organic solvent, the organic solvent may be an ester 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, alkyloxyacetates (e.g., methyl alkyloxyacetate, alkyloxyacetate, alkyloxyacetate, alkyloxybutyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate) 3-alkyloxypropionate 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-alkyloxypropionate 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 (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 A 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 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 toluene, xylene, anisole, and other aromatic hydrocarbons, 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 isobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0040] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. 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.

[0041] 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. Alternatively, the above content may be 100% by mass.

[0042] The developing solution may contain other components as well. Other components include, for example, known surfactants and known defoaming agents.

[0043] [Method of supplying developing solution] There are no particular restrictions on the method of supplying the developer, as long as the desired pattern can be formed. These methods include immersing the substrate on which the film has been formed in the developer, paddle development where the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred. Alternatively, the process may involve continuously supplying the developer solution through a straight nozzle, spinning the substrate to remove the developer solution from the substrate, spin-drying, and then continuously supplying the developer solution again through a straight nozzle, spinning the substrate to remove the developer solution from the substrate. This process may be repeated multiple times. Furthermore, possible methods for supplying the developer during the developing process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a nearly stationary state on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0044] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0045] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0046] [Rinsing solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0047] When the rinse solution contains an organic solvent, the organic solvent can be an ester 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, alkyloxyacetates (e.g., alkyloxyacetate methyl, alkyloxyacetate ethyl acetate, alkyloxyacetate butyl (e.g., methoxyacetate methyl, methoxyacetate ethyl, methoxyacetate butyl, ethoxyacetate methyl, ethoxyacetate methyl, ethoxyacetate methyl ethyl acetate, 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.)), alkyl 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxy Tyl, 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 E 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 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 toluene, xylene, anisole, and other aromatic hydrocarbons, 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 isobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0048] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. 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.

[0049] If the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of the organic solvent, more preferably 70% or more by mass of the organic solvent, and even more preferably 90% or more by mass of the organic solvent. Alternatively, the rinsing solution may contain 100% by mass of the organic solvent.

[0050] The rinse solution may contain other ingredients as well. Other components include, for example, known surfactants and known defoaming agents.

[0051] [Method of supplying rinse solution] There are no particular restrictions on the method of supplying the rinsing solution, as long as a desired pattern can be formed. These methods include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution onto it, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinse solution, the removal of non-image areas, and manufacturing efficiency, there are methods for supplying the rinse solution using shower nozzles, straight nozzles, spray nozzles, etc. A method of continuous supply using a spray nozzle is preferred, and from the viewpoint of the penetration of the rinse solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. In other words, the rinsing step is preferably a step of supplying the rinsing solution to the exposed film using a straight nozzle or a continuous supply step, and more preferably a step of supplying the rinsing solution using a spray nozzle. Furthermore, possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0052] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0053] <Heating process> The pattern obtained by the development process (or the pattern after rinsing, if a rinsing process is performed) is preferably subjected to a heating process in which the pattern obtained by the development process (a component made of a resin composition) is heated. In other words, the method for producing a cured product according to the polyimide-containing composition of the present invention may include a heating step of heating the pattern obtained by the developing step. Furthermore, the method for producing a cured product according to the polyimide-containing composition of the present invention may also preferably include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by an application step, and it is even more preferable to include a heating step of heating a film obtained by an application step without performing a developing step. During the heating process, resins such as polyimide precursors undergo cyclization to become resins such as polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in specific resins or other crosslinking agents also proceeds. The heating temperature (maximum heating temperature) in the heating process is preferably 375°C or lower, more preferably 350°C or lower, even more preferably 300°C or lower, and can also be 250°C or lower. The lower limit of the heating temperature is preferably 160°C or higher, more preferably 170°C or higher, and even more preferably 180°C or higher. By adjusting heating conditions such as heating temperature and heating time during the heating process, it is possible to adjust the glass transition temperature of the polyimide-containing portion. Specifically, it is believed that heating at a higher temperature for a longer period of time increases the ring closure rate of the polyimide, thereby raising the glass transition temperature.

[0054] The heating step is preferably a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0055] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0056] The starting temperature for 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 starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying. For example, it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0057] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0058] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 240°C or less.

[0059] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is best carried out for a short time, from about 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferable. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be performed in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, the mixture may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / minute.

[0060] The heating process is preferably carried out in a low-oxygen atmosphere by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process are not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0061] <Post-development exposure process> The pattern obtained by the development process (or the pattern after rinsing, if a rinsing process is performed) may be subjected to a post-development exposure process in which the pattern after the development process is exposed, either in place of the heating process or in addition to the heating process. In other words, the method for producing a cured product according to the polyimide-containing composition of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product according to the polyimide-containing composition of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure process, for example, reactions such as the cyclization of polyimide precursors, etc., by exposure to a photobase generator, and the elimination of acid-degradable groups by exposure to a photoacid generator can be accelerated. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The exposure amount in the post-development exposure step is 50 to 20,000 mJ / cm², converted to exposure energy at the wavelength to which the photosensitive compound is sensitive. 2 Preferably, the concentration is 100 to 15,000 mJ / cm². 2 It is preferable that it be so. The post-development exposure step can be performed, for example, using the light source from the exposure step described above, and it is preferable to use broadband light.

[0062] <Preparing substrate B> A method for manufacturing a bonded body using the polyimide-containing composition of the present invention includes the step of preparing a substrate B having a surface equipped with wiring terminals.

[0063] The form of substrate B may be a wafer or a chip. These can be selected according to the desired design of the bonded structure.

[0064] [Circuit board B] Circuit board B has wiring terminals. Hereafter, the wiring terminals on circuit board B will also be referred to as wiring terminal B.

[0065] The thickness of substrate B is preferably 0.1 to 5 mm, and more preferably 0.2 to 1 mm. In the bonded body obtained by the bonding process described later, at least a portion of the wiring terminal B is electrically bonded to the wiring terminal A on the substrate A described above.

[0066] The material used for substrate B is not particularly limited, but the same material as that used for substrate A described above is preferred. Furthermore, the preferred embodiment of wiring terminal B is the same as the preferred embodiment of wiring terminal A. Substrate B may have an electronic circuit region including an electronic circuit. Furthermore, the electronic circuit may have elements such as semiconductors. It is also preferable that the electronic circuit is electrically connected to the wiring terminals. When substrate B is a wafer, its size can be 100 mm or more in diameter (or maximum diameter if substrate B is not circular). For larger substrates, it is preferable to have a size of 200 mm or more, and more preferably 250 mm or more. There is no particular upper limit, but it is preferable to have a size of 2,000 mm or less. When substrate B is a chip, the size is preferably such that the diameter (or maximum diameter if substrate B is not circular) is 7 mm or more, more preferably 8 mm or more, and even more preferably 10 mm or more. As an upper limit, for example, it is preferably 50 mm or less, more preferably 30 mm or less, and even more preferably 20 mm or less.

[0067] <Second polyimide-containing portion formation process> A method for manufacturing a bonded body using the polyimide-containing portion forming composition of the present invention preferably further includes a second polyimide-containing portion forming step, in which a second polyimide-containing portion is formed on the surface of the substrate B having the wiring terminals, prior to the bonding step. The second polyimide-containing portion formation step can be carried out, for example, by the same method as the polyimide-containing portion formation step for substrate A described above. In the second polyimide-containing portion formation step, the polyimide-containing portion formation composition of the present invention may be used, or other known polyimide-containing portion formation compositions may be used, but it is preferable to use the polyimide-containing portion formation composition of the present invention. However, when the polyimide-containing portion forming composition of the present invention is used in the second polyimide-containing portion forming step, the composition of the polyimide-containing portion forming composition of the present invention used in the second polyimide-containing portion forming step and the composition of the polyimide-containing portion forming composition used in the polyimide-containing portion forming step for substrate A may be the same or different. A preferred embodiment of the second polyimide-containing portion is the same as the preferred embodiment of the polyimide-containing portion formed in the substrate A described above. In the bonding process described later, it is believed that the adhesion of the bonded body will be improved by bonding the second polyimide-containing portion and the polyimide-containing portion formed on the substrate A described above in such a way that they are in contact in at least a portion of the area.

[0068] Furthermore, when forming a second polyimide-containing portion, it is preferable that the glass transition temperature of the second polyimide-containing portion is lower than the bonding temperature in the bonding process. From the viewpoint of increasing the maximum peel resistance, the glass transition temperature of the second polyimide-containing portion is preferably 30°C or more lower than the bonding temperature in the bonding process, more preferably 50°C or more lower, and even more preferably 70°C or more lower. Furthermore, it is preferable that the glass transition temperature of the second polyimide-containing portion is 30°C or more higher than the bonding temperature in the bonding process.

[0069] [Flattening process] In a method for manufacturing a bonded body using the polyimide-containing portion forming composition of the present invention, it is preferable to include a planarization step between the polyimide-containing portion forming step and the bonding step, in which the surface of the polyimide-containing portion of the substrate A is planarized. In the bonding process described later, it is preferable that the planarized polyimide-containing portion of base material A and the surface of base material B (or the surface of a second polyimide-containing portion which may also be planarized) are joined in contact.

[0070] As a result of the planarization described above, it is preferable that the wiring terminals A on the substrate A are exposed from the polyimide-containing portion. The above planarization may be carried out by physical polishing such as cutting, mechanical polishing, grinding, plasma treatment, and laser ablation, or by chemical polishing such as CMP (Chemical Mechanical Polishing). Alternatively, these methods can be combined, such as performing CMP after cutting. Specifically, for example, one method involves cutting the surface of the polyimide-containing portion with a diamond cutting tool to expose the new surface of the polyimide-containing portion and the wiring terminal A. By performing a planarization process on the substrate A between the wiring terminal A and the polyimide-containing portion so that the wiring terminal A is exposed, it becomes possible to expose the leading edge of the wiring terminal A by simultaneously planarizing the wiring terminal A and the polyimide-containing portion. Surface planing can be performed, for example, using a surface planer. Examples of surface planers include those with a diamond cutting tool mounted on a spindle, such as the DISCO DFS8910, DFS8960, DAS8920, and DAS8930 (all product names).

[0071] -TTV- In the planarization process, it is preferable that the polyimide-containing portion is planarized together with the wiring terminal A. The degree of planarization is preferably such that the TTV (Total Thickness Variation) of the polyimide-containing portion and the wiring terminal A is 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. In this invention, TTV refers to the arithmetic mean of the film thickness differences (T1-T2) of the remaining sections. The TTV is calculated by dividing the area 1 mm or more inward from the edge of the polyimide-containing portion into 2 mm square sections (if the area of ​​the polyimide-containing portion is too small to be divided into 2 mm square sections, the entire area 1 mm or more inward from the edge of the polyimide-containing portion is considered one section), measuring the maximum thickness (T1) and minimum thickness (T2) between one surface and the other surface for each section, calculating the film thickness difference (T1-T2) for each section, assigning a hierarchy to the sections in descending order of film thickness difference (T1-T2), excluding a number of section groups corresponding to 10% of the total number of sections (rounded down if decimal places exist) in descending order of film thickness difference starting from the top-ranked section (largest film thickness difference), and excluding a number of section groups corresponding to 10% of the total number of sections (rounded down if decimal places exist) in descending order of film thickness difference starting from the lowest-ranked section (smallest film thickness difference), and so on. In this specification, the term "partition evaluation TTV" may be used when referring specifically to the TTV of the polyimide-containing portion as defined herein. By keeping the TTV of the polyimide-containing portion below the above upper limit, the film thickness becomes generally uniform, and the adhesion to the substrate B is improved.

[0072] -Ra- The polyimide-containing portion of the present invention preferably has a surface roughness Ra of 10 nm or more and 1.5 μm or less on the side 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, even more preferably 200 nm or less, even more preferably 150 nm or less, and even more preferably 120 nm or less. By making the surface roughness of the polyimide-containing portion equal to or greater than the above lower limit, an anchoring effect can be activated to improve adhesion to substrate B. Furthermore, by keeping the surface roughness below the above upper limit, it is possible to effectively suppress the occurrence of defects such as voids caused by bubbles or other imperfections during bonding with substrate B.

[0073] When forming a second polyimide-containing portion on substrate B, it is preferable to include a second planarization step between the second polyimide-containing portion formation step and the bonding step, in which the surface of the second polyimide-containing portion is planarized. The second planarization step can be carried out in the same manner as the planarization step in substrate A described above.

[0074] [Joining process] A method for manufacturing a bonded body using the polyimide-containing composition of the present invention includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion to the surface of the substrate B having the wiring terminals. If the substrate B has a second polyimide-containing portion, the bonding step is a step of bonding the surface of the substrate A having the polyimide-containing portion to the surface of the substrate B having the second polyimide-containing portion.

[0075] Through bonding, wiring terminal A on board A and wiring terminal B on board B are electrically connected. In the above bonding process, one preferred embodiment of the present invention is that the electrodes included in the surface of substrate A having a polyimide-containing portion and the electrodes on the surface of substrate B having the wiring terminals are bonded in direct contact. In other words, it is also preferable that neither wiring terminal A nor wiring terminal B has a conductive passage. In the present invention, since the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature, adhesion and electrical connectivity between substrate A and substrate B can be ensured even when a conductive passage is not used.

[0076] The joining is preferably carried out by means including heating, and more preferably by means including heating and pressurizing. The 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. This temperature is preferably near the melting point of the conductive passage, taking into consideration the need to melt the conductive passage and enable bonding between electrodes, as described above. The heating time in the joining process 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. A practical upper limit is 30 minutes or less. The heating environment is not particularly limited, but it is preferable to carry it out under a reduced pressure atmosphere while mechanically pressurizing the polyimide-containing portion. The atmospheric pressure should be 1 × 10⁻⁶. -5 Preferably, mbar or more, 1 × 10 -4 It is more preferable that it be mbar or greater, 5 × 10 -4It is even more preferable that it be mbar or higher. As an upper limit, it is preferably 0.1 mbar or less, and 1 × 10⁻⁶ -2 It is more preferable that it be less than or equal to mbar, 5 × 10 -3 It is even more preferable that it be less than or equal to 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. As an upper limit, it is practical to be 100 kN or less. The equipment used in the bonding process is not particularly limited, but equipment used for reflow soldering of electronic components can be suitably used.

[0077] Furthermore, it is preferable that the substrate A, which contains the polyimide, is preheated to 70°C or higher during the bonding process. Furthermore, if substrate B includes a second polyimide-containing portion, it is preferable that the temperature of substrate B is preheated to 70°C or higher. The above temperature is preferably 70°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit of the above temperature is not particularly limited, but is preferably 130°C or lower. The above embodiment makes it possible to reduce the cycle time of the joining process. Furthermore, the fluidity of the polyimide-containing portion during bonding may improve, potentially leading to an increase in the maximum peel resistance.

[0078] [Other processes] Furthermore, the method for manufacturing a bonded body using the polyimide-containing composition of the present invention does not preclude the inclusion of other steps between the steps specified above. In addition, although the explanation has mainly focused on an example in which substrate A and substrate B are joined by facing each other face to face as a joining step, a configuration in which multiple substrates B are arranged in parallel with substrate A and bonded together is also possible. Alternatively, a configuration in which substrates A and B of a suitable thickness are placed side by side and their sides are joined together is also possible.

[0079] <Example of a manufacturing method for a jointed body> The following describes an example of a method for manufacturing a joined body, using diagrams. Figure 2 is a schematic cross-sectional diagram illustrating a part of the process when bonding a substrate using a method for manufacturing a bonded body according to one embodiment of the present invention. First, a substrate A (base substrate) 1 is prepared, on which an electronic circuit region 8 is arranged on a silicon wafer 1x and electrodes 31 (wiring terminals A) are attached thereto (Figure 2(a)). An electronic circuit 81, composed of a conductor or semiconductor, is already formed inside the electronic circuit region 8 of the substrate A1. The method for forming the electronic circuit is not particularly limited and can be formed by conventional methods. Furthermore, the structure and components of the electronic circuit are not particularly limited, and examples include a transistor and a wiring structure that connects it to the electrodes.

[0080] The resin composition is applied to the electrode-laid surface (the surface having the electronic circuit region) P0 of the substrate A1 to form a component (resin composition layer) 4 made of the resin composition (Figure 2(b)). In this state, the resin composition layer may be heated and dried (drying step). Alternatively, after drying, the resin composition layer 4 may be patterned by photolithography or ion sputtering.

[0081] Subsequently, in this embodiment, the resin composition layer 4 is heated to promote cyclization and harden to form a polyimide-containing portion 41 (Figure 2(c)). This forms a polyimide-containing portion-distributed substrate 1y on substrate A1 with the polyimide-containing portion 41 disposed thereon. As in this example, the polyimide-containing portion 41 may shrink compared to the resin composition layer 4 due to hardening. Although the figures are slightly exaggerated, the shrinkage rate is not particularly limited, and a smaller shrinkage rate is acceptable, or it may not shrink at all due to hardening. Furthermore, although the substrate A shown in the figure has only an electrode 31 as a wiring terminal A, a conductive passage may be formed on the electrode 31. The conductive passage may be formed in the substrate A from the beginning, or the polyimide-containing portion may be patterned before curing, and the conductive passage may be created in the patterned portion by plating or other means.

[0082] In the polyimide-containing substrate 1y of this embodiment, the heights h1 and h2 of the electrodes 31 vary. Also, the surface 4a of the polyimide-containing portion is wavy and not flat. In this embodiment, by performing flattening, the variations in the height of the electrodes 31 are eliminated, the leading surface is exposed, and the surface of the polyimide-containing portion is also flattened. By performing this planarization, it is believed that the adhesion of the substrate will be improved. Furthermore, it is believed that the connectivity between wiring terminals will be improved even without forming a conductive path.

[0083] Figure 3 shows the polyimide-containing substrate (laminated structure) 1z after planarization. The tip 31a of the electrode 31 is exposed on the surface 4b of the polyimide-containing portion, and the entire surface 4b of the polyimide-containing portion is planarized.

[0084] A substrate B is prepared separately for the laminate (planarized polyimide-containing substrate) 1z (Figure 4(a)). Substrate B2 comprises a silicon wafer 2x having through-hole electrodes 2y, a circuit wiring region 8 having circuit wiring 81 disposed thereon, and electrodes 32 (wiring terminals B) formed within the circuit wiring region 8. In this embodiment, a second polyimide-containing portion 42 is also formed on the surface of substrate B having the wiring terminals B, and its surface 2a is planarized in the same way as the surface of the polyimide-containing portion 41 on substrate A. The formation and planarization of the second polyimide-containing portion 42 can be carried out by the same method as the formation and planarization of the polyimide-containing portion 41. As described above, since the surfaces of the polyimide-containing portion 41 and electrode 31 of substrate A, and the surfaces of the second polyimide-containing portion 42 and electrode 32 of substrate B are both flattened, electrical connectivity is improved even when there is no conductive path, as in this embodiment. At this time, the electrode 31 portion of the laminate and the electrode 32 provided on the substrate B2 are aligned (positioned) so that they come into contact. In this case, if at least one of the polyimide-containing portion 41 and the second polyimide-containing portion 42 contains a migration inhibitor, even if misalignment occurs in this alignment, it is possible to suppress the migration of metal from the electrode 31 (electrode 32) to the polyimide-containing portion 41 (second polyimide-containing portion 42), thereby improving the dielectric strength. In the wiring terminal B, a conductive passage may also be formed on the electrode 32. The conductive passage may be formed in the substrate B from the beginning, or the second polyimide-containing portion may be patterned before hardening, and the conductive passage may be created in the patterned portion by plating or other means.

[0085] Next, in this embodiment, the aligned substrate B2 and the laminate 1z are joined by contacting them at the bonding surface P1 via the polyimide-containing portion 41 and the second polyimide-containing portion 42 (Figure 4(b)). This forms a bonded body 100 in which two substrates are joined together. In the bonded body 100, electrodes 31 and 32 are electrically joined (joining process). Simultaneously, the heating described above softens the polyimide-containing portion 41, causing the surface 4b of the polyimide-containing portion of the laminate 1z to bond with the surface 2a of the substrate B (the flattened surface of the second polyimide-containing portion 42), thereby forming the bonded body 100. In this invention, since the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding process, the polyimide-containing portion is sufficiently softened, resulting in excellent adhesion. This allows for an electrical connection between substrate A and substrate B, as well as a secure and stable fixation between them.

[0086] In a preferred embodiment of the present invention, the flatness of the polyimide-containing surface 4b and the second polyimide-containing surface 2a of the laminate 1z is high, so a dense and accurate contact state with the substrate B2 can be obtained 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.

[0087] (Method of manufacturing a device) The device according to the present invention comprises a joint obtained by a method for manufacturing a joint using the polyimide-containing portion forming composition of the present invention. The method for manufacturing a semiconductor device of the present invention includes the method for manufacturing a bonded structure of the present invention. The devices according to the present invention include semiconductor devices, electronic devices, and the like, and are preferably semiconductor devices or electronic devices. Examples of devices include those described in "Illustrated Guide to All About Cutting-Edge Semiconductor Packaging Technology" edited by the Semiconductor New Technology Research Group, Kogyo Chosakai, pp. 8-19, 110-114, 160-165, and "Illustrated Guide to All About Surface Treatment Technology" edited by the Surface Optics Research Institute, Kanto Gakuin University, Kogyo Chosakai, pp. 32-41, 56-59. Specifically, examples include using the aforementioned polyimide-containing portion as an adhesive film to replace the underfill between chips, and using the aforementioned polyimide-containing portion as a die bonding film to fix the chips. Furthermore, the polyimide-containing composition for forming parts of the present invention can be applied to a wide range of applications, including the mounting of LED (light-emitting diode) elements, the mounting of optical elements in flat panel displays, and the mounting of power semiconductor packages. Furthermore, for example, the polyimide-containing composition for forming the present invention can be suitably used in the three-dimensional packaging of semiconductor devices equipped with through-silicon vias (TSVs). Figure 5 is a schematic cross-sectional view of a three-dimensional mounting device. In this embodiment, a laminate 101, in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked, is arranged on a wiring substrate 120. The plurality of semiconductor elements 101a to 101d are all made of semiconductor wafers such as silicon substrates. The laminate 101 has a structure in which a semiconductor element 101a without through electrodes and semiconductor elements 101b to 101d having through electrodes 102b to 102d are connected by flip-chip connections. The connection pads on the semiconductor element side having 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 each semiconductor element 101a to 101d. The manufacturing method of the bonded body according to the present invention can be used as the manufacturing method of this laminate. That is, for example, at least one (preferably all) of the resin layers 110 can be a polyimide-containing portion made of the polyimide-containing portion forming composition of the present invention described above. A surface electrode 120a is provided on one side of the wiring board 120. An insulating layer 115 on which a rewiring layer 105 is formed is disposed between the wiring board 120 and the laminate (substrate / substrate laminate) 101. One end of the rewiring layer 105 is connected to an electrode pad formed on the side 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 the surface electrode 120a of the wiring board 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 polyimide-containing portion forming composition of the present invention can also be used for bonding 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 also formed between the insulating layer 115 and the wiring board 120. The polyimide-containing portion forming composition of the present invention can also be used for bonding the insulating layer 115 to the wiring board 120. That is, for example, the resin layer 110b can be made into the polyimide-containing portion described above.

[0088] (Details of the resin composition) The details of each component contained in the polyimide-containing composition of the present invention will be described below. The polyimide-containing composition of the present invention preferably contains at least one resin selected from the group consisting of polyimides and polyimide precursors (hereinafter also referred to as "specific resin"), and a solvent, and more preferably contains a polyimide precursor and a solvent. Furthermore, the polyimide-containing composition of the present invention preferably further contains a photosensitive compound. Examples of photosensitive compounds include photopolymerization initiators and photoacid generators, with photopolymerization initiators being preferred.

[0089] <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. Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. When a specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator as described below, and more preferably contains a radical polymerization initiator as described below and a radical crosslinking agent as described below. Furthermore, it may optionally contain a sensitizer as described below. A negative-type photosensitive film can be formed from such a resin composition of the present invention. Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups. When a specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. From such a resin composition of the present invention, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0090] [Polyimide precursor] The polyimide precursor used in this invention is not particularly limited in type, but it is preferable that it contains repeating units represented by the following formula (2). [ka] In formula (2), A 1 and A 2Each of these independently represents an oxygen atom or -NH-, and R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0091] A in equation (2) 1 and A 2 Each of these independently represents either an oxygen atom or -NH-, with the oxygen atom being preferred. R in equation (2) 111 -Ar- and -Ar-L-Ar- are examples of divalent organic groups. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of 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 combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and aromatic group, the hydrocarbon group of the ring member may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. The preferred ranges for these are as described above.

[0092] R 111 It is preferable that the polyimide precursor is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One type of diamine may be used, or two or more types may be used. Specifically, the diamine is preferably a diamine containing 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 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 hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0093] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -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.

[0094] Diamines specifically include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or 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 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine , bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester 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,Examples include 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)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 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'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0095] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0096] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0097] R 111 From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting 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 that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0098] Also, R 111From the perspective of i-line transmittance, it is preferably a divalent organic group represented by the following formula (51) or formula (61). Particularly, from the perspectives of i-line transmittance and ease of acquisition, it is more preferably a divalent organic group represented by formula (61). Formula (51)

Chemical formula

Chemical formula

[0099] R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * independently represents a bonding site with another structure. [ka] In formula (5), R 112 The linking group is a single bond or a divalent linking group, preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, and -NHCO-, and a group selected from combinations thereof; more preferably a single bond or a C1-C3 alkylene group 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-.

[0100] R 115 Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R 115 The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. Tetracarboxylic acid dianhydrides are preferably represented by the following formula (O). [ka] In formula (O), R 115 R represents a tetravalent organic group. 115 The preferred range of R in equation (2) is 115 This is synonymous with the same thing, and the preferred range is also similar.

[0101] 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, and 2,2 ',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, Examples include 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of these having 1 to 6 carbon atoms.

[0102] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0103] In equation (2), R 111 and R 115It is also possible that at least one of them has an OH group. More specifically, R 111 Examples include residues of bisaminophenol derivatives.

[0104] R in equation (2) 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R 113 and R 114 It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having ethylenically unsaturated bonds are preferred. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0105] [ka]

[0106] In equation (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In equation (III), * represents a bonding site with another structure. In equation (III), R 201 This represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxy group. Suitable R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the above-mentioned group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating or other patterned arrangements. The preferred configuration of the number of repeating ethylene oxy groups in these groups is as described above.

[0107] In equation (2), R 113 If R is a hydrogen atom, 114 If the atom 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.

[0108] In equation (2), R 113 and R 114 At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group are preferred.

[0109] Also, the polyimide precursor preferably has a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0110] Also, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0111] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude. Formula (2-A)

Chemical formula

[0112] A 1 、A 2 、R 111 、R 113 and R 114 each independently represent A in formula (2) 1 、A 2 、R 111 、R113 and R 114 This is synonymous with the same thing, and the preferred range is also similar. R 112 R in equation (5) 112 This is synonymous with the same thing, and the preferred range is also similar.

[0113] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0114] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above 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 above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0115] 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 degree of molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of molecular weight dispersion is the value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, if the resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0116] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to the other bonding chains.

[0117] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. Fluorine atoms are, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0118] - silicon atom - From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have a silicon atom. The silicon atom is preferably contained in R in the repeating unit represented by, for example, formula (4) described later. 131 in the repeating unit represented by formula (4) described later, and more preferably contained as an organically modified (poly) siloxane structure in R in the repeating unit represented by formula (4) described later. 131 Also, the above silicon atom or the above organically modified (poly) siloxane structure may be contained in the 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.

[0119] - ethylenically unsaturated bond - From the viewpoint of the film strength of the resulting organic film, it is preferable for the polyimide to have an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the main chain end or in the side chain, but it is preferably in the side chain. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by formula (4) described later. 132 or in R in the repeating unit represented by formula (4) described later. 131 and is preferably contained in R in the repeating unit represented by formula (4) described later. 132 or in R in the repeating unit represented by formula (4) described later. 131 and more preferably contained as a group having an ethylenically unsaturated bond in R in the repeating unit represented by formula (4) described later. Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by formula (4) described later. 131 in the repeating unit represented by formula (4) described later.131 It is more preferable to be included as a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having a vinyl group which may be substituted and is directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (IV), etc.

[0120]

Chemical formula

[0121] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.

[0122] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the carbon number of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the repeating number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a group combining two or more of these. Further, as the alkylene group having 2 to 12 carbon atoms, any of an alkylene group represented by a linear, branched, cyclic or combination thereof may be used. As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.

[0123] Among these, R 21 is preferably a group represented by any of the following formula (R1) to formula (R3), and more preferably a group represented by formula (R1).

Chemical formula

[0124] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0125] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0126] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimides may have polymerizable groups other than those having ethylenically unsaturated bonds. Polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having an ethylenically unsaturated bond include, for example, R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0127] -Polar Conversion Group- Polyimides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. 131 , R 132 It is found at the ends of polyimides, etc.

[0128] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, regarding the acid groups contained in polyimide, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​shall be those calculated using ACD / ChemSketch®. Alternatively, values ​​published in the "Revised 5th Edition Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan may be referred to. Furthermore, if the acidic group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. The polyimide preferably contains at least one of the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0129] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. Polyimides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0130] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, R 132 This represents a tetravalent organic group. If it has polymerizable groups, the polymerizable groups are R 131 and R 132 It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups are equivalent to 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 is equivalent to formula (4).

[0131] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. R 131 R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is 111 Similar examples are given, and the preferred range is also similar. Also, R 131Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. 111 Examples include:

[0132] R 131 It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine that does not contain an aromatic ring.

[0133] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0134] R 132 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is 115 Similar examples are given, and the preferred range is also similar. For example, R 115 The four bonds of the tetravalent organic group, as exemplified above, bond with the four -C(=O)- parts in formula (4) above to form a fused ring.

[0135] Also, R 132 Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor.115 Examples include: From the standpoint of the strength of the organic film, R 132 It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0136] R 131 and R 132 It is also preferable that at least one of them has an OH group. More specifically, R 131 As examples, 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) are listed as preferred examples, R 132 As such, (DAA-1) to (DAA-5) above can be cited as more preferable examples.

[0137] Furthermore, it is preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

[0138] Furthermore, to improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0139] Furthermore, in order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-captives such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, 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 Examples include -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, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0140] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate can be measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure was found at 1377 cm⁻¹. -1 The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. -1 Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula. Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0141] Polyimides are all of the same type R 131 or R 132 It may include the repeating unit represented by the above formula (4), and may include two or more different types of R 131 or R 132 The polyimide may also contain repeating units represented by the above formula (4). In addition to the repeating units 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 units represented by the above formula (2).

[0142] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0143] 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 flexural resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of molecular weight dispersion of the polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit set for the degree of molecular weight dispersion of the polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimides are treated as a single resin are, respectively, within the above ranges.

[0144] [Method for producing polyimide precursors, etc.] Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents mentioned above 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 agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyimide precursors, 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 determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0145] -End-capturing agent- In the production method of polyimide precursors, etc., it is preferable to encapsulate the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When encapsulating the carboxylic acid anhydride and acid anhydride derivative remaining at the resin ends, examples of end encapsulants include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and from the standpoint of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferable. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, 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 phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenolic compounds.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, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants. Furthermore, when sealing the amino groups at the ends of the resin, it is possible to seal them with compounds having functional groups that can react with the amino groups. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0146] -Solid precipitation- The production of polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. The resulting solid is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the process may include a step for removing ionic impurities using an ion exchange resin.

[0147] [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. Furthermore, 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 it contains two or more specific resins, it is preferable that the total amount is within the above range.

[0148] Furthermore, the resin composition of the present invention preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above). 115 Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0149] <Other resins> The resin composition of the present invention may include the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a polymerizable compound with a high polymerizable value of 20,000 or less weight-average molecular weight (for example, the molar amount of polymerizable groups in 1g of resin is 1 × 10⁻⁶) -3 By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved. Furthermore, other resins can be added to the resin composition as filler dispersants. In such embodiments, known filler dispersants can be used as other resins without particular limitation.

[0150] If 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, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on 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. Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even 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 above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0151] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0152] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups. Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0153] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred. Furthermore, 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 a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

[0154] 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.

[0155] 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.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0156] Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane, among others. Examples of polyfunctional acrylates and methacrylates, as well as mixtures thereof, include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated; urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193; polyester acrylates as described in Japanese Unexamined Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490; and epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid. Compounds described in paragraphs 0254 to 0257 of Japanese Unexamined Patent Publication No. 2008-292970 are also suitable. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond.

[0157] In addition, other preferred radical crosslinking agents besides those mentioned above include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent No. 4364216, etc., as well as cardo resins.

[0158] Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, as well as vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesion Society of Japan, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0159] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be preferably used, and these contents are incorporated herein.

[0160] Furthermore, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylateing them, as described in Japanese Patent Publication No. 10-062986 with specific examples of formulas (1) and (2), can also be used as radical crosslinking agents.

[0161] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Publication No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein by reference.

[0162] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0163] Examples of commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethylene oxy chains, manufactured by Sartomer; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains, also manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxy chains; and urethane. Examples include Ligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0164] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0165] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0166] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing, as well as excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0167] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in 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, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional 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 in which the molecular weight of the polyethylene glycol chain is approximately 200. From the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0168] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to 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.

[0169] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0170] [Other crosslinking agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process. Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used. As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents. 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 glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0171] Examples of compounds containing at least one alkoxymethyl group and acyloxymethyl group in the present invention include compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

[0172] [ka]

[0173] R 100 This represents an alkyl group or acyl group. R 101 and R 102 Each of these independently represents a monovalent organic group and may be bonded to each other to form a ring.

[0174] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted for an aromatic group include compounds with the following general formula.

[0175] [ka]

[0176] 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, R 103 This includes hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or groups that decompose upon the action of an acid to produce alkali-soluble groups (for example, groups that are eliminated by the action of an acid, -C(R4 ) 2COOR 5 The group represented by (R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 The symbol indicates a group that is removed by the action of an acid. R 105 Each independently represents an alkyl group or an alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Groups that decompose under the action of acid to produce alkali-soluble groups, groups that are eliminated under the action of 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 Examples include: In the formula, R 36 ~R 39 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 These elements may be joined together to form a ring. The alkyl group described above 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 described above may be linear or branched. The above 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 above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above 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-mentioned 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 those described above for preferred embodiments of alkyl and aryl groups. The above 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. Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

[0177] R 01 and R 02 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0178] Groups that decompose upon the action of an acid to produce alkali-soluble groups, or groups that are eliminated upon the action of an acid, are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, tertiary alkyl ester groups and acetal groups.

[0179] The following structures are examples of compounds containing an alkoxymethyl group. Compounds containing an acyloxymethyl group are examples of compounds obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. The following compounds are examples of compounds containing an alkoxymethyl group or acyloxymethyl group in the molecule, but are not limited to these.

[0180] [ka]

[0181] [ka]

[0182] The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

[0183] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0184] Specific examples of urea-based crosslinking agents include, for example, glycoluryl-based crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monoethoxymethylated glycoluryl, diethoxymethylated glycoluryl, triethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Ethylene urea-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.

[0185] Specific examples of benzoguanamine 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, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0186] In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably 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''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0187] Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both 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. Examples include 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.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0188] Furthermore, the resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0189] - 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 temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

[0190] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably with 2 to 15 repeating units.

[0191] 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, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (all product names, manufactured by DIC Corporation), Licaresin® BEO-20E, Licaresin® BEO-60E, Licaresin® HBE-100, Licaresin® DME-100, Licaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples include 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, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

[0192] [ka]

[0193] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0194] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0195] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 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 include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0196] -Benzoxazine compounds (compounds containing a benzoxazolyl group)- Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

[0197] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0198] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agents may be present by one type or by two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0199] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. It is particularly preferable that it contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that interacts with a photoexcited sensitizer to generate active radicals.

[0200] The photoradical polymerization initiator is present in a wavelength range of approximately 240-800 nm (preferably 330-500 nm) at a concentration of at least approximately 50 L·mol. -1 ·cm -1 It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0201] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165-0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

[0202] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0203] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0204] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, 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) can be used.

[0205] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0206] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, whose maximum absorption wavelength is matched to a light source of wavelength such as 365 nm or 405 nm, can also be used, and this is incorporated herein by reference.

[0207] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

[0208] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0209] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0210] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein by reference.

[0211] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linking group in their molecule.

[0212] [ka]

[0213] Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arcules NCI-730, NCI-831, and ADEKA Arcules NCI-930 (manufactured by ADEKA Corporation). Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds with the following structures can also be used. [ka]

[0214] As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the details of which are incorporated herein by reference.

[0215] As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505, which are incorporated herein by reference.

[0216] Furthermore, oxime compounds containing a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 2013-164471, the details of which are incorporated herein by reference.

[0217] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein by reference. Another example of an oxime compound having a nitro group is ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0218] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0219] As a photo-radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photo-polymerization initiators include the compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0220] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. OX1 An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. OX1 Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0221] 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 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. R X2 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. R X3 ~R X14 Each of these independently represents a hydrogen atom or a substituent; However, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0222] In the above formula, R X12 R is an electron-withdrawing group, X10 , R X11 , R X13 , R X14 It is preferable that it is a hydrogen atom.

[0223] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, which are incorporated herein by reference.

[0224] The most preferred oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as described in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0225] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal 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 their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0226] Further 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, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, and the use of a metallocene compound or an oxime compound being even more preferred.

[0227] Furthermore, photoradical polymerization initiators can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones fused with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethylketal. In addition, compounds represented by the following formula (I) can also be used.

[0228] [ka]

[0229] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. I01 is a group represented by formula (II), or R I00 It is the same group as R I02 ~R I04 Each of these is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0230] [ka]

[0231] In the formula, R I05 ~R I07 This is R in equation (I) above. I02 ~R I04 It is the same as this.

[0232] Furthermore, the photoradical polymerization initiator may be a compound described in paragraphs 0048-0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0233] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher 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, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1-7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0234] If a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range. Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[0235] -Thermal polymerization initiator- The resin composition according to the present invention may also preferably contain a thermal polymerization initiator. While thermal polymerization initiators can be selected according to the type of polymerizable compound, thermal radical polymerization initiators are preferred. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy, thereby initiating or accelerating the polymerization reaction of polymerizable compounds. Furthermore, the photopolymerization initiators mentioned above may also have the function of initiating polymerization upon heat, and may be added as thermal polymerization initiators.

[0236] Examples of thermal polymerization initiators include known azo compounds and known peroxide compounds. Examples of azo compounds include azobis compounds. Azo compounds may or may not have a cyano group. Examples of peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like. Commercially available thermal polymerization initiators can also be used, including V-40, V-601, and VF-096 from Fujifilm Wako Pure Chemical Industries, Ltd., and Perhexyl O, Perhexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Perkmill D, Perkmill D-40, Perkmill D-40MB, Perkmill H, Perkmill P, and Perkmill ND from NOF Corporation. Furthermore, as thermal radical polymerization initiators, specific examples include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0237] The content of the thermal polymerization initiator in the resin composition is preferably 0.05% to 10% by mass, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.5% to 3% by mass, based on the total solid content of the composition. The resin composition (especially the second resin composition) may contain one thermal polymerization initiator alone or two or more. When two or more are included, it is preferable that their total amount be within the above range.

[0238] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenones, Michlaz ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyrans, and indigos. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. 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 (7-(diethylamino)coumarin-3-carboxylate ethyl), N-Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-Tolyldiethanolamine, N-phenylethanolamine, 4-Morpholinobenzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Examples include amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details regarding the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0239] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0240] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0241] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0242] If 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, based on 100 parts by mass of the total solid content of the resin composition of the present invention. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total is within the above range.

[0243] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator refers to a compound that generates at least one of a Brønsted acid and a Lewis acid upon irradiation with light in the 200 nm to 900 nm range. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, and more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, the photoacid generator is preferably capable of generating acid upon photosensitization. Preferred examples of acids that are generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diphosphate esters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0244] Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oximesulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like. From the viewpoint of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the mechanical properties of the formed film, oxime esters are preferred.

[0245] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxypolyamino compound. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds are substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By including such quinone diazide compounds, it is possible to obtain resin compositions that are sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of mercury lamps, which are common ultraviolet rays.

[0246] Specifically, hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisO CP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, T riML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industries), BIR-OC, BI P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Examples of such materials include, but are not limited to, Asahi Organic Chemicals Industry Co., Ltd.'s products: 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc.

[0247] Examples of amino compounds include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0248] Furthermore, specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0249] Among these, it is preferable that the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.

[0250] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of resin. This range of quinone diazide compound content is preferable because it allows for higher sensitivity by obtaining a contrast between the exposed and unexposed areas. Furthermore, sensitizers and other additives may be added as needed.

[0251] The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but it is preferably an oxime sulfonate compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later.

[0252] [ka]

[0253] In equation (OS-1), X 3 X represents an alkyl group, an alkoxy group, or a halogen atom. 3 If there are multiple instances, they may be the same or different. (See above X) 3 The alkyl and alkoxy groups in may have substituents.3 The alkyl group in is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 In X, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. 3 In this mixture, chlorine atoms or fluorine atoms are preferred as halogen atoms. In formula (OS-1), m3 represents an integer between 0 and 3, preferably 0 or 1. When m3 is 2 or 3, multiple X 3 They may be the same or different. In equation (OS-1), R 34 represents an alkyl or aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl halide group having 6 to 20 carbon atoms.

[0254] In equation (OS-1), m3 is 3, and X 3 The group is a methyl group, X 3 The substitution position is the ortho position, R 34 Compounds in which the group is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group are particularly preferred.

[0255] Specific examples of oximesulfonate compounds represented by formula (OS-1) include the following compounds described in paragraphs 0064-0068 of Japanese Patent Publication No. 2011-209692 and paragraphs 0158-0167 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0256] [ka]

[0257] In formula (OS-103) ~ formula (OS-105), R s1 R represents an alkyl group, aryl group, or heteroaryl group, and there may be multiple R groups. s2 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and there may be multiple Rs. s6 Each of these independently represents a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group, or alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6. In formula (OS-103) ~ formula (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the above may have substituents known within the range in which the effects of the present invention can be obtained.

[0258] In formula (OS-103) ~ formula (OS-105), R s2 R is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. There may be two or more R in the compound. s2 It is preferable that one or two of these are alkyl groups, aryl groups, or halogen atoms, more preferably that one is an alkyl group, aryl group, or halogen atom, and particularly preferably that one is an alkyl group and the rest are hydrogen atoms. s2 The alkyl or aryl group represented by may have substituents known within the range that the effects of the present invention can be obtained. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

[0259] In formulas (OS-103) to (OS-105), ns represents either 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) ~ formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the above may have substituents. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0260] Furthermore, the compound represented by formula (OS-103) is particularly preferably a compound represented by formula (OS-106), formula (OS-110), or formula (OS-111), the compound represented by formula (OS-104) is particularly preferably a compound represented by formula (OS-107), and the compound represented by formula (OS-105) is particularly preferably a compound represented by formula (OS-108) or formula (OS-109). [ka]

[0261] In formula (OS-106) ~ formula (OS-111), R t1 R represents an alkyl group, an aryl group, or a heteroaryl group. t7 R represents a hydrogen atom or a bromine atom. t8 R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. t9 R represents a hydrogen atom, halogen atom, methyl group, or methoxy group. t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 This represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0262] In formula (OS-106) ~ formula (OS-111), R t8 This represents a hydrogen atom, a C1-C8 alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, preferably a C1-C8 alkyl group, more preferably a C1-C8 alkyl group, even more preferably a C1-C6 alkyl group, and particularly preferably a methyl group.

[0263] In formula (OS-106) ~ formula (OS-111), R t9 This represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and is preferably a hydrogen atom. R t2 This represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E,Z) of the oxime may be either one or a mixture. Specific examples of oximesulfonate compounds represented by formulas (OS-103) to (OS-105) above include the compounds described in paragraphs 0088 to 0095 of Japanese Patent Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference.

[0264] Other preferred embodiments of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

[0265] [ka]

[0266] In formula (OS-101) or formula (OS-102), R u9R represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or heteroaryl group. u9 A more preferable embodiment is that R is a cyano group or an aryl group. u9 A more preferable embodiment is one in which the group is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a This represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 Each of these independently represents an alkyl group or an aryl group.

[0267] In formula (OS-101) or formula (OS-102), R u1 ~R u4 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of these may bond to each other to form a ring. In this case, the ring may fused to form a fused ring with the benzene ring. u1 ~R u4 Preferably, R is a hydrogen atom, a halogen atom, or an alkyl group. u1 ~R u4 A configuration in which at least two of them bond to each other to form an aryl group is also preferred. u1 ~R u4 A configuration in which all of these atoms are hydrogen atoms is preferred. Each of the above substituents may have further substituents.

[0268] The compound represented by the above formula (OS-101) is more preferably the compound represented by the formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture of both. Specific examples of compounds represented by formula (OS-101) include those described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [ka] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Chemical Co., Ltd.).

[0269] Furthermore, compounds represented by the following structural formula are also preferred examples. [ka]

[0270] Examples of organic halogenated compounds include those described in Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-32070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-70243, Japanese Unexamined Patent Publication No. 63-298339, and MPHutt, "Jurnal of Heterocyclic Chemistry" 1 (No. 3), (1970), and the contents of these publications are incorporated herein by reference. In particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds are preferred examples. More preferably, s-triazine derivatives having at least one mono, di, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine Liazin, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl) Phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0271] Examples of organoborate compounds include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Publication No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98. Proceeding April Organic borates as described in "19-22, 1998, Chicago," etc., organoboron sulfonium complexes or organoboron oxosulfonium complexes as described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, organoboron iodonium as described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553 Examples include organoboron phosphonium complexes described in Japanese Patent Publication No. 9-188710, organoboron transition metal coordination complexes described in Japanese Patent Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014, and the contents of these are incorporated herein by reference.

[0272] Examples of disulfone compounds include those described in Japanese Patent Publication No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

[0273] Examples of the above onium salt compounds include diazonium salts described in SISchlesinger, Photogr.Sci.Eng., 18,387 (1974) and TSBal et al, Polymer, 21,423 (1980), ammonium salts described in U.S. Patent No. 4,069,055 and Japanese Patent Publication No. 4-365049, phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056, and iodonium salts described in European Patent Nos. 104 and 143, U.S. Patent Nos. 339,049 and 410,201, Japanese Patent Publication No. 2-150848 and Japanese Patent Publication No. 2-296514. Sulfonium salts as described in the specifications of European Patents No. 370,693, 390,214, 233,567, 297,443, and 297,442; U.S. Patents No. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827; German Patents No. 2,904,626, 3,604,580, and 3,604,581; JVCrivello Examples include selenonium salts described in et al, Macromolecules, 10(6), 1307 (1977) and JVCrivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), as well as onium salts such as arsonium salts and pyridinium salts described in CSWen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and these contents are incorporated herein by reference.

[0274] Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III). [ka] In equation (RI-I), Ar 11Z represents an aryl group having 20 or fewer carbon atoms, which may have 1 to 6 substituents. Preferred substituents include C1-C12 alkyl groups, C2-C12 alkenyl groups, C2-C12 alkynyl groups, C6-C12 aryl groups, C1-C12 alkoxy groups, C1-C12 aryloxy groups, halogen atoms, C1-C12 alkylamino groups, C2-C12 dialkylamino groups, alkylamide groups of the alkyl group having 1 to 12 carbon atoms or arylamide groups of the aryl group having 6 to 20 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups, and C1-C12 thioaryl groups. 11 - represents a monovalent anion, and includes halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. From the standpoint of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In formula (RI-II), Ar 21 Ar 22 Each of these independently represents an aryl group having 1 to 20 carbon atoms, which may have 1 to 6 substituents. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group, alkylamide or arylamide groups having 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z21 -R represents a monovalent anion, and includes halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. From the standpoint of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R 31 , R 32 , R 33 Each of these represents an aryl group or alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, which may each have 1 to 6 substituents independently. Preferably, from the viewpoint of reactivity and stability, it is an aryl group. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms in each alkyl group independently, alkylamide groups or arylamide groups having 1 to 12 carbon atoms in each alkyl group, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. 31 - ∫ represents a monovalent anion, which can be a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, or sulfate ion. From the standpoint of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, or carboxylate ion are preferred.

[0275] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0276] The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, relative to the total solid content of the resin composition. The photoacid generator may be used alone or in combination of multiple types. In the case of a combination of multiple types, it is preferable that their total amount is within the above range. Furthermore, it is preferable to use it in combination with a sensitizer in order to impart photosensitivity to the desired light source.

[0277] <Base Generator> The resin composition of the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. Preferred base-generating agents for the resin composition of the present invention include thermal base-generating agents and photobase-generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages. The base generator can be either an ionic or nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base-generating agent according to the present invention, and known base-generating agents can be used. Examples of known base-generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific examples of nonionic base-generating compounds include those represented by formulas (B1), (B2), or (B3). [ka]

[0278] In equations (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Each of these is independently an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb 1 and Rb 2 They cannot become hydrogen atoms at the same time. Also, Rb 1 , Rb 2 and Rb 3 None of these have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply when the bonded carbon atom forms a carbonyl group, i.e., when it forms an amide group together with the nitrogen atom.

[0279] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3Preferably, at least one of these components contains a cyclic structure, and more preferably, at least two contain cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a 5-membered ring or a 6-membered ring, with a 6-membered ring being more preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0280] More specifically, Rb 1 and Rb 2 The group is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that provides the effects of the present invention. Rb 1 and Rb 2 These may be bonded to each other to form a ring. A preferred ring is a 4-7 member nitrogen-containing heterocycle. Rb 1 and Rb 2 In particular, it is preferable that the alkyl group is a linear, branched, or cyclic alkyl group which may have substituents (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have substituents (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a cyclohexyl group which may have substituents.

[0281] Rb 3Examples include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb 3 It may further have substituents to the extent that it exhibits the effects of the present invention.

[0282] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2). [ka]

[0283] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 These are, respectively, Rb in equation (B1). 1 and Rb 2 It is the same as this. Rb 13The group is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents within a range that provides the effects of the present invention. In particular, Rb 13 An aryl alkyl group is preferred.

[0284] Rb 33 and Rb 34 Each of these is independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably 1 to 8, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably 2 to 8, and still more preferably 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

[0285] Rb 35 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

[0286] Compounds represented by formula (B1-1) are preferred, as are compounds represented by formula (B1-1a). [ka]

[0287] Rb 11 and Rb 12Rb in equation (B1-1) 11 and Rb 12 It is synonymous with [the above]. Rb 15 and Rb 16 The group is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and still more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and still more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and still more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and still more preferably with 7 to 11 carbon atoms), with a hydrogen atom or a methyl group being preferred. Rb 17 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

[0288] [ka]

[0289] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen and carbon atoms, and having 3 or more atoms on the linking chain pathway. N1 and R N2 Each of these independently represents a monovalent organic group.

[0290] In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that links these linked objects in the shortest possible distance (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4. [ka]

[0291] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0292] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1). [ka]

[0293] In formula (N1), R N1 and R N2 Each of these independently represents a monovalent organic group, RC1 represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0294] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

[0295] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and is preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include an aliphatic hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with an aliphatic hydrocarbon group being preferred. N1 and R N2 Using an aliphatic hydrocarbon group is preferable because it results in a base with high basicity. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and they may also have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0296] R N1 and R N2Examples of aliphatic hydrocarbon groups that constitute the linear alkyl group include linear or branched alkyl groups, cyclic alkyl groups, groups relating to a combination of linear alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched alkyl groups are preferably those having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, and the like. The cyclic alkyl group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. The group comprising the combination of a linear alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. Examples of groups comprising the combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. In particular, from the perspective of raising the boiling point of the decomposition product bases described later, R N1 and R N2 A C5-C12 alkyl group is preferred. However, in formulations where adhesion to a metal (e.g., copper) layer is important, a cyclic alkyl group or a C1-C8 alkyl group is preferred.

[0297] R N1 and R N2These may be linked together to form a cyclic structure. In forming a cyclic structure, oxygen atoms, etc., may be present in the chain. Also, R N1 and R N2 The cyclic structure formed may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1), and examples include a pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, and morpholine ring, with pyrroline ring, pyrrolidine ring, piperidine ring, and morpholine ring being preferred.

[0298] R C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

[0299] As a protecting group, a protecting group that decomposes upon the action of an acid or a base is preferred, and a protecting group that decomposes with an acid is particularly preferred.

[0300] Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methyloxymethyl (MOM) and ethyloxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0301] There are no specific requirements for the divalent linking group constituting L, but hydrocarbon groups are preferred, and aliphatic hydrocarbon groups are more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, it is preferable to have a divalent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, or a group which is a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylenealkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0302] The preferred linking group L is specifically a linear or branched linear alkylene group, a cyclic alkylene group, a group relating to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group. The linear or branched linear alkylene group is preferably composed of 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. The combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

[0303] The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group is preferably one with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0304] Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

[0305] [ka]

[0306] 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.

[0307] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0308] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0309] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0310] If the resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less. One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range.

[0311] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0312] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0313] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0314] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0315] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0316] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0317] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0318] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0319] 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, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0320] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0321] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0322] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method.

[0323] The resin composition of the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total number is within the above range.

[0324] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0325] [Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062-0073 of Japanese Patent Publication No. 2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060-0061 of Japanese Patent Publication No. 2014-191252, the compounds described in paragraphs 0045-0052 of Japanese Patent Publication No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and the compounds described in paragraphs 0067-0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. It is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0326] [ka]

[0327] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

[0328] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0329] Furthermore, other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0330] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content falls within the above range.

[0331] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the film.

[0332] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0333] Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

[0334] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0335] Specific examples of migration inhibitors include the following compounds.

[0336] [ka]

[0337] If the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition of the present invention.

[0338] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0339] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0340] Specific polymerization inhibitor compounds include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine monocerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso -1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and compounds described in paragraphs 0031-0046 of International Publication No. 2015 / 125469 may also be used, and this is incorporated herein by reference.

[0341] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.

[0342] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0343] <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, an acid scavenger refers to a compound that can capture generated acids when 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, such as primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides, with primary amines, secondary amines, tertiary amines, and ammonium salts being preferred, and secondary amines, tertiary amines, and ammonium salts being more preferred. Preferred acid scavengers 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 linkage; and aniline derivatives having a hydroxyl group and / or an ether linkage. When an onium structure is present, the acid scavenger is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than the acid generated by the acid generator.

[0344] 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]nona-5-ene, and 1,8-diazabicyclo[5,4,0]undeker7-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 linkage include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether linkage include N,N-bis(hydroxyethyl)aniline.

[0345] 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-methylammonium hydroxide Examples include methylhexylamine, 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, etc.

[0346] These acid scavengers may be used individually or in combination of two or more types. The composition according to the present invention may or may not contain an acid scavenger. If it does contain an acid scavenger, the amount of acid scavenger is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[0347] The ratio of acid generator to acid scavenger used is preferably 2.5 to 300 in molar ratio. Specifically, a molar ratio of 2.5 or higher is preferred from the viewpoint of sensitivity and resolution, and 300 or lower is preferred from the viewpoint of suppressing the decrease in resolution due to the thickening of the relief pattern over time from exposure to heat treatment. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0348] The resin composition of the present invention may also contain fillers. The filler is preferably thermally conductive. The filler may also be electrically insulating, semiconductor, 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 that filler is 1.0 × 10⁻⁶. 11 Preferably, it is Ω·cm or larger, and 3.0 × 10 11 It is more preferable that the value be Ω·cm or greater, and 1.0 × 10 12 It is particularly preferable that the resistivity be Ω·cm or greater. Furthermore, the upper limit of the volume resistivity is not particularly limited, but for example, 1.0 × 10⁻⁶ 18 The following values ​​are preferable: Ω·cm. On the other hand, in the case of semiconductors and conductive fillers, there is no particular lower limit to the volume resistivity of the filler, but practically speaking, it is 1.0 × 10⁻⁶. -7 It is greater than or equal to Ω·cm. Furthermore, the upper limit of the volume resistivity is 1.0 × 10⁻⁶. 11 It is preferable that the value is less than Ω·cm.

[0349] The thermal diffusivity of the filler is, for example, 5.0 × 10⁻⁶ -7 m 2 s -1 Preferably, it is 1.0 × 10 -6 m 2 s -1 It is more preferable that the above be 2.0 × 10 -6 m 2 s -1 It is even more preferable that the above be the case, 3.0 × 10 -6 m 2 s -1The above is particularly preferable. Furthermore, there is no particular upper limit to the thermal diffusivity of the filler, but for example, 1.0 × 10 -4 m 2 s -1 The following is preferable:

[0350] The density of the filler is, for example, 4.0 g / cm³. 3 Preferably, it is 3.0 g / cm³. 3 The following is more preferable. Furthermore, the lower limit of the filler density is not particularly limited, but for example, 1.0 g / cm³. 3 The above is preferable. Furthermore, if the filler is porous or has voids or cavities, such as being a porous or hollow particle, the density of the filler in this specification refers to the density of the solid component among the components constituting the filler.

[0351] Preferably, the filler includes an electrically insulating material. The electrically insulating filler material is, for example, an electrically insulating ceramic 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 and carbon compounds include silicon carbide. Examples of boron compounds include metallic borides such as titanium boride. Other carbon compounds include carbon substrate materials where σ bonds are dominant, such as diamond. Examples of the above composite compounds include mineral-based ceramics such as magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, bentonite, and pyroferrite. Furthermore, the electrically insulating filler material may be a metal hydroxide such as magnesium hydroxide or aluminum hydroxide.

[0352] Among these, from the viewpoint of thermal conductivity and other factors, the filler material preferably contains at least one of the following: ceramics made of nitrogen compounds, ceramics made of metal oxides, and metal hydroxides. Furthermore, the filler material preferably contains at least one selected from the group consisting of, for example, boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide, and aluminum hydroxide. In particular, it is especially preferable that the filler material contains at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide, and it is even more preferable that it contains at least one of boron nitride, aluminum nitride, silicon nitride, and aluminum oxide. Note that the boron nitride may have any of the following structures: c-BN (cubic structure), w-BN (wurtzite structure), h-BN (hexagonal structure), r-BN (rhombohedral structure), t-BN (random structure), etc. Boron nitride can be spherical or flaky, and both can be used. Furthermore, the IX-3 series and other products manufactured by Nippon Shokubai can also be suitably used.

[0353] Examples of conductive filler materials include carbon substrate materials where π bonds are dominant, such as graphite, carbon black, carbon fiber (pitch-based, PAN-based), carbon nanotubes (CNTs), and carbon nanofibers (CNFs). Other filler materials may include metals such as silver, copper, iron, nickel, aluminum, and titanium, as well as alloys such as stainless steel (SUS). Furthermore, conductive metal oxides such as zinc oxide doped with heterogeneous elements, and conductive ceramics such as ferrite can also be used as filler materials.

[0354] The filler may be composed of semiconductor or conductive thermally conductive particles coated or surface-treated with an electrically insulating material such as silica. This configuration makes it easier to individually control thermal conductivity and electrical insulation, thus facilitating adjustment of these properties. For example, methods for forming a silica film on the surface include the water glass method and the sol-gel method.

[0355] These fillers can be used individually or in combination of two or more. Furthermore, there are no particular limitations on the shape of the fillers; various shapes can be used, such as fibrous, plate-like, flaky, rod-like, spherical, tubular, curved plate-like, and needle-like forms.

[0356] The filler may be subjected to surface treatments such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, or oxidation treatment. Examples of surface treatment agents used include polyols, aluminum oxide, aluminum hydroxide, silica (silicon dioxide), hydrated silica, alkanolamines, stearic acid, organosiloxanes, zirconium oxide, hydrogen dimethicone, silane coupling agents, and titanate coupling agents. Among these, silane coupling agents are preferred.

[0357] Regarding the size of the filler, the average particle diameter of the filler is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. Furthermore, the average particle size of the filler is preferably 0.01 μm or larger, more preferably 0.05 μm or larger, even more preferably 0.1 μm or larger, and particularly preferably 0.3 μm or larger. The "average particle size" of the filler can be determined by observing the filler in the polyimide-containing portion with a scanning electron microscope (SEM) and observing the parts where the filler particles are not aggregated (primary particles). The average particle diameter can be calculated as the average of the diameters of the minimum inclusion circles for the apparent contour of each particle observed by SEM. Specifically, it can be described by the method described in the examples below.

[0358] The filler may contain a granular mixture in which at least two groups of particles with different particle sizes are mixed. The "particle size" of a certain particle group is determined in the same way as the "particle size" of the filler. With this configuration, smaller particles fill the spaces between larger particles, reducing the spacing between fillers and increasing the contact points compared to a case containing only a single-diameter filler, thus improving thermal conductivity. For example, when two groups of particles with different particle sizes 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 different groups of particles with different particle sizes are contained in the granular mixture that serves as the filler.

[0359] When there are multiple peaks in the particle size distribution of the filler, the peak-to-particle-size ratio (the ratio of particle sizes corresponding to the peak peaks) between at least two peaks is preferably 1.5 to 50. The lower limit is preferably 2 or more, and more preferably 4 or more. The upper limit is preferably 40 or less, and more preferably 20 or less. If the above peak ratio is within the above range, it becomes easier for small-diameter fillers to occupy the spaces between large-diameter fillers while suppressing large-diameter fillers from becoming coarse particles. Furthermore, for at least two peaks, the peak intensity ratio of the larger-grained peak to the smaller-grained peak is preferably 0.2 to 5.0. The lower limit is preferably 0.2 or higher, and more preferably 0.5 or higher. The upper limit is preferably 5.0 or lower, and more preferably 3.0 or lower.

[0360] The filler content is preferably 10% by mass or more, and more preferably 30% by mass or more, relative to the total solid content of the resin composition. The above content is not particularly limited, but from the viewpoint of processability by lithography, it is preferably 90% by mass or less, and more preferably 75% by mass or less. If the resin composition contains fillers, any statement regarding the content of components other than fillers that means "relative to the total solids content of the resin composition" shall be read as "relative to the total mass of the resin composition excluding the fillers."

[0361] The proportion of particles with a particle size of 0.5 to 15 μm in the total filler is preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit of this proportion can be 100% by mass or 99% by mass or less. This proportion is preferably 99% by mass or less, and more preferably 95% by mass or less.

[0362] As described above, fillers can be used individually or in combination of two or more types, and if two or more types of fillers are included, it is preferable that their total amount is within the above range.

[0363] <Other additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-flocculation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, it is preferable that their total amount is 3% by mass or less of the solid content of the resin composition of the present invention.

[0364] [Surfactants] Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0365] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the amount of liquid used can be further improved. Specifically, when forming a film using a coating solution to which a composition containing a surfactant has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0366] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (all manufactured by DIC Corporation), Florard FC430, FC431, FC171, Novec FC4430, FC4432 (all manufactured by 3M Corporation) Examples include Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Corporation), etc. As fluorine-based surfactants, compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503 may also be used, and the contents of these are incorporated herein. Block polymers can also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Publication No. 2011-89090, the details of which are incorporated herein by reference. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka]

[0367] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorine-based surfactants can also be obtained by using fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0368] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0369] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BIC Chemie Co., Ltd.).

[0370] Examples of hydrocarbon-based surfactants include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T, etc. (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0371] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0372] Examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymers Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0373] Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0374] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0375] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after application.

[0376] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0377] 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% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[0378] [UV absorber] The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate, while examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0379] Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2-hydroxy(hydroxy) Examples include bis(hydroxyphenyl)triazine compounds such as c-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0380] In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the amount of ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition of the present invention.

[0381] [Organotitanium compounds] The resin composition of this embodiment may contain an organotitanium compound. By including an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0382] Examples of usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate). II) Tetraalkoxy titanium 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 tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)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-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0383] In particular, from the viewpoint of achieving better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0384] When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0385] [Antioxidant] The composition of the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group within the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent Publication No. 6268967 may also be used as antioxidants, and this information is incorporated herein by reference. Additionally, the compositions of the present invention may optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100 to 250°C or at 80 to 200°C in the presence of an acid / base catalyst, thereby removing the protecting group.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219, the contents of which are incorporated herein by reference. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by formula (3).

[0386] [ka]

[0387] In general formula (3), R 5 R represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 k represents a 1-4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2-10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0388] The compound represented by formula (3) suppresses the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins. Furthermore, it can suppress metal oxidation by providing rust prevention to metal materials.

[0389] Since it can act on both resin and metal materials simultaneously, k is more preferably an integer between 2 and 4. 7Examples of these groups include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may also have substituents. Among these, alkyl ether groups and -NH- groups are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- groups are more preferred from the viewpoint of interaction with the resin and metal adhesion due to metal complex formation.

[0390] Examples of compounds represented by general formula (3) include the following, but are not limited to the structures shown below.

[0391] [ka]

[0392] [ka]

[0393] [ka]

[0394] [ka]

[0395] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. 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 their total amount falls within the above range.

[0396] [Anti-coagulation agent] The resin composition of this embodiment may optionally contain an anti-flocculation agent. Examples of anti-flocculation agents include sodium polyacrylate.

[0397] In the present invention, one type of anticoagulant may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-flocculation agent. If it does contain an anti-flocculation agent, the amount of the anti-flocculation agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition of the present invention.

[0398] [Phenol compounds] The resin composition of this embodiment may optionally contain phenolic compounds. Examples of phenolic compounds 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, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0399] In this invention, a single phenolic compound may be used alone, or two or more compounds may be used in combination. The composition of the present invention may or may not contain a phenolic compound. If it does contain a phenolic compound, the content of the phenolic compound 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, based on the total solid content of the composition of the present invention.

[0400] [Other polymer compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0401] In this invention, the other polymer compounds may be used individually or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. If other polymer compounds are included, 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, based on the total solid content mass of the composition of the present invention.

[0402] <Properties of resin compositions> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm 2 / s~12,000mm 2 / s is preferred, and 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500mm 2 / s~8,000mm 2 / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm 2 If the rate is 1 / s or higher, it is easy to coat the film thickness required for, for example, as an insulating film for rewiring, and 12,000 mm 2 If the rate is less than or equal to / s, an excellent coating film can be obtained on the coated surface.

[0403] <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 it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the storage container.

[0404] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm (parts per million) by mass, 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 excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0405] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0406] When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content 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. In particular, the amount 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 chl...

Claims

1. A step of preparing a substrate A having a surface equipped with wiring terminals, A polyimide-containing portion forming step, in which a polyimide-containing portion is formed on the surface of the substrate A that has the wiring terminals, A step of preparing a substrate B having a surface equipped with wiring terminals, and A polyimide-containing portion forming composition used in a method for manufacturing a bonded body, which includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion to the surface of the substrate B having the wiring terminals, The polyimide-containing portion is a member formed from the polyimide-containing portion forming composition, The polyimide-containing portion formation step includes applying the polyimide-containing portion formation composition to the surface of the substrate A having the wiring terminals and heating it, The heating temperature in the aforementioned heating is 200°C or higher. The glass transition temperature of the polyimide-containing portion is 30°C or more lower than the bonding temperature in the bonding process. Composition for forming polyimide-containing parts.

2. A composition for forming a polyimide-containing portion according to claim 1, comprising a polyimide precursor and a solvent.

3. A composition for forming a polyimide-containing portion according to claim 1 or 2, further comprising a migration inhibitor.

4. The polyimide-containing composition according to claim 1 or 2, wherein the glass transition temperature of the polyimide-containing portion is 350°C or less.

5. The polyimide-containing composition according to claim 1 or 2, wherein the bonding temperature in the bonding step is 380°C or lower.

6. The polyimide-containing portion forming composition according to claim 1 or 2, wherein the form of the substrate A is a wafer.

7. The polyimide-containing portion forming composition according to claim 1 or 2, wherein the form of the substrate B is a chip.

8. The polyimide-containing portion forming composition according to claim 1 or 2, wherein the form of the substrate B is a wafer.

9. The polyimide-containing portion forming composition according to claim 1 or 2, wherein the temperature of the substrate A having the polyimide-containing portion is preheated to 70°C or higher during the bonding process.

10. The polyimide-containing portion forming composition according to claim 1 or 2, further comprising a planarization step between the polyimide-containing portion forming step and the bonding step, wherein the surface of the polyimide-containing portion of the substrate A is planarized.

11. The polyimide-containing portion forming composition according to claim 10, wherein the planarization step is performed by physical polishing.

12. The polyimide-containing portion forming composition according to claim 10, wherein the planarization step is performed by chemical polishing.

13. The polyimide-containing portion forming composition according to claim 1 or 2, wherein in the bonding step, an electrode included in the surface of the substrate A having the polyimide-containing portion and an electrode on the surface of the substrate B having the wiring terminals are bonded together in direct contact.

14. The polyimide-containing portion forming composition according to claim 1 or 2, further comprising a second polyimide-containing portion forming step of forming a second polyimide-containing portion on the surface of the substrate B having the wiring terminals, prior to the bonding step.

15. A composition for forming a polyimide-containing portion according to claim 1 or 2, further comprising a photosensitive compound.

16. The polyimide-containing composition according to claim 1 or 2, wherein the heating temperature in the heating is 375°C or lower.

17. A step of preparing a substrate A having a surface equipped with wiring terminals, A polyimide-containing portion forming step, in which a polyimide-containing portion is formed on the surface of the substrate A that has the wiring terminals, A step of preparing a substrate B having a surface equipped with wiring terminals, and The process includes joining the surface of substrate A having a polyimide-containing portion to the surface of substrate B having the wiring terminals, The polyimide-containing portion formation step includes applying the polyimide-containing portion formation composition to the surface of the substrate A having the wiring terminals and heating it, The heating temperature in the aforementioned heating is 200°C or higher. A method for manufacturing a bonded body, wherein the glass transition temperature of the polyimide-containing portion is 30 degrees Celsius or more lower than the bonding temperature in the bonding process.

18. A joint obtained by the manufacturing method described in claim 17.

19. A method for manufacturing a device, comprising the method for manufacturing a bonded body as described in claim 17.

20. A device comprising the joint described in claim 18.

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