A method for manufacturing a bonded body, a method for manufacturing a semiconductor device, and a resin composition.

Abstract

Provided are: a joined body manufacturing method including a step for preparing a substrate A having a surface with projection parts and a substrate B having a wiring terminal, a step for forming a filler-containing layer which includes a binder and a filler on the surface of the substrate A with the projection parts, a step for planarizing the filler-containing layer together with the projection parts and exposing at least a portion of the projection parts from the filler-containing layer, and thereby obtaining a laminate, and a step for joining the surface of the laminate having the filler-containing layer and at least a portion of the wiring terminal of the substrate B; a method for manufacturing a semiconductor device comprising the joined body obtained by the manufacturing method; and a resin composition for use in the manufacturing method.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a bonded body, a method for manufacturing a semiconductor device, and a resin composition. [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 (Cross-Owned Cubic) element with the structure shown in Figure 1 above, the daughter chip 1 and mother chip 2 are connected and fixed with solder bumps 93, and then underfill 94 is filled into 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. However, there are components such as wire bonding pads 97b around the COC, and it is not easy to fill the underfill without contaminating these surfaces at all. Furthermore, with the increasing integration of circuits, the pitch of solder bumps is becoming narrower and narrower. It is becoming difficult to reliably fill the space between them with underfill. Furthermore, such underfill is used solely to mitigate physical damage and improve connection reliability. In electronic devices, dissipating heat generated from electronic circuits and other components is extremely important from the standpoint of suppressing abnormal operation of semiconductors and other elements, preventing performance degradation, and extending their lifespan. In other words, there was room for further consideration regarding the improvement of heat dissipation performance through underfill in conventionally used underfill.

[0006] Therefore, the present invention aims to provide a method for manufacturing a bonded body having a filler-containing layer with excellent thermal conductivity, a method for manufacturing a semiconductor device having the bonded body obtained by the above manufacturing method, and a resin composition used in the above manufacturing method. [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 with a protrusion, and a substrate B having wiring terminals. A step of forming a filler-containing layer containing a binder and a filler on the surface of the substrate A having the above-mentioned protrusions, The process of flattening the filler-containing layer together with the protrusions to expose at least a portion of the protrusions from the filler-containing layer and to obtain a laminate, and The process includes joining the surface of the laminate having the filler-containing layer to at least a portion of the wiring terminals of the substrate B. A method for manufacturing a composite body. <2> The step of forming the filler-containing layer includes applying a resin composition comprising at least one resin selected from the group consisting of a binder and a binder precursor, and a filler, onto the surface of the substrate A having the protrusions. <1> A method for manufacturing the joint described above. <3> The step of forming the above-mentioned filler-containing layer includes, after the above application, heating the composition at a temperature of 150 to 300°C. <2> A method for manufacturing the joint described above. <4> The above resin composition includes, as the resin, at least one resin selected from the group consisting of cyclized resins and their precursors. <2> or <3> A method for manufacturing the joint described above. <5> The TTV of the filler-containing layer in the above laminate is 10 μm or less. The TTV is calculated by dividing the region 1 mm or more inward from the edge of the filler-containing layer into 2 mm square sections, measuring the maximum thickness (T1) and the minimum thickness (T2) between one surface and the other surface in each section, calculating the film thickness difference (T1-T2) for each section, ranking the sections in descending order of film thickness difference (T1-T2), excluding 10% of the total number of sections in descending order of film thickness difference from the top section, and excluding 10% of the total number of sections in descending order of film thickness difference from the bottom section, and the arithmetic mean of the film thickness differences (T1-T2) for each of the remaining sections. <1> ~ <4> A method for manufacturing a joint described in any one of the following. <6> The above-mentioned protrusion contains metal. <1> ~ <5> A method for manufacturing a joint described in any one of the following. <7> The above metal includes at least one metal selected from the group consisting of copper, tin, and nickel. <6> A method for manufacturing the joint described above. <8> The above-mentioned protrusion is a protrusion comprising at least a layer containing copper and a layer containing tin. <1> ~ <7> A method for manufacturing a joint described in any one of the following. <9> The binder contained in the filler-containing layer is an insulating binder. <1> ~ <8> A method for manufacturing a joint described in any one of the following. <10> The binder contained in the filler-containing layer comprises at least one group selected from the group consisting of vinyl groups, acrylic groups, and methacrylic groups. <1> ~ <9> A method for manufacturing a joint described in any one of the following. <11> The above filler includes at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide. <1> ~ <10> A method for manufacturing a joint described in any one of the following. <12> The volume resistivity of the above filler is 1.0 x 10 11 It is greater than or equal to Ω·cm. <1> ~ <11> A method for manufacturing a joint described in any one of the following. <13> The average particle diameter of the above filler is 10 μm or less, and the above average particle diameter is the average value of the diameter of the minimum inclusion circle relative to the apparent contour of each particle. <1> ~ <12> A method for manufacturing a joint described in any one of the following. <14> In the process of obtaining the above laminate, the planarization is performed by cutting. <1> ~ <13> A method for manufacturing a joint described in any one of the following. <15> The bonding temperature in the above bonding process is 300°C or lower. <1> ~ <14> A method for manufacturing a joint described in any one of the following. <16> The thermal diffusivity of the filler-containing layer in the resulting bonded structure is 2.0 × 10⁻⁶. -7 m 2 s -1 That's all. <1> ~ <15> A method for manufacturing a joint described in any one of the following. <17> <1> ~ <16> A method for manufacturing a semiconductor device, comprising a bond obtained by the method for manufacturing a bond described in any one of the following. <18> <1> ~ <16> A resin composition used for forming the filler-containing layer in the method for manufacturing a bonded body described in any one of the above. [Effects of the Invention]

[0008] The present invention provides a method for manufacturing a bonded body having a filler-containing layer with excellent thermal conductivity, a method for manufacturing a semiconductor device having the bonded body obtained by the above manufacturing method, and a resin composition used in the above manufacturing method. [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 diagram illustrating the process of joining substrates using a method for manufacturing a bonded body according to one embodiment of the present invention, shown in a cross-sectional view. [Figure 3] This is a schematic diagram illustrating the process of joining substrates using a manufacturing method for a bonded body according to one embodiment of the present invention (continuation of Figure 2). [Figure 4] This is a schematic diagram illustrating the process of joining substrates using a manufacturing method for a bonded body according to one embodiment of the present invention (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] (Method of manufacturing the joint) The present invention provides a method for manufacturing a bonded body, comprising the steps of: preparing a substrate A having a surface with protrusions and a substrate B having wiring terminals; forming a filler-containing layer containing a binder and a filler on the surface of the substrate A having the protrusions; flattening the filler-containing layer together with the protrusions to expose at least a portion of the protrusions from the filler-containing layer and obtain a laminate; and joining the surface of the laminate having the filler-containing layer to at least a portion of the wiring terminals on the substrate B.

[0012] In the present invention, by incorporating a filler into the resin layer to form a filler-containing layer, a layer with excellent thermal diffusivity can be formed. Furthermore, by incorporating fillers, the CTE (coefficient of thermal expansion) of the filler-containing layer can be lowered, making it possible to bring the CTE of the substrate and the CTE of the filler-containing layer closer together. This is expected to have effects such as suppressing warping of the bonded structure and suppressing delamination in the bonded structure. Furthermore, processes using NCF (Non-Conductive Film) have been considered for some time. Specifically, this involves pre-laminating the solder electrodes on the daughter chip with NCF and then bonding them to the mother chip. For example, the daughter chip (first substrate) is brought into contact with the mother chip (second substrate), then heated to melt the solder and connect it to the electrodes on the mother chip (second substrate), while simultaneously heating and softening the adhesive film to bond and fix the two together. However, if there are variations in the height of the electrodes on the mother chip, for example, voids and poor bonding between the daughter chip and mother chip may occur due to insufficient flow of NCF. Furthermore, lithography is used to remove the resin layer on the pillars, but this has problems such as increasing the number of steps. In addition, because the height of the protrusions such as pillars on the pillar substrate is not uniform, voids occur at lower positions of the protrusions (or some kind of treatment is required, such as needing material to fill the voids), which has been a problem. In this invention, the height of the protrusions and the resin layer (filler-containing layer) can be aligned to some extent by flattening before joining. This makes it possible to manufacture a joined body that is less prone to peeling and in which the generation of voids is suppressed. The following describes each step in the method for manufacturing the bonded body of the present invention.

[0013] <Preparation process> The present invention provides a method for manufacturing a bonded body, which includes a step (preparation step) of preparing a substrate A having a surface with a protrusion and a substrate B having wiring terminals. In the preparation process, substrates A and B may be manufactured or obtained by means of purchase or other means.

[0014] [Substrate A] Substrate A has a surface with a protrusion. 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 protrusions on substrate A are preferably pillar electrodes. Furthermore, the above-mentioned protrusions preferably contain metal, more preferably contain at least one metal selected from the group consisting of tin (Sn), gold (Au), silver (Ag), copper (Cu), 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 contain 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 protrusion may be a protrusion comprising multiple different members. For example, the substrate may have a portion used as an electrode (hereinafter also referred to as "electrode") made of a metal such as copper, silver, gold, or an alloy containing one or more of these, and a portion used as solder (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 may be formed on a metal layer such as copper, and the electrode and the conducting passage may be in series to form a single protrusion. Among these, it is preferable that the above-mentioned protrusions comprise at least a layer containing copper and a layer containing tin. An example of a substrate A having such protrusions is the substrate b) used in the embodiment of the present invention. In substrate b), a conductive passage made of tin is formed on an electrode made of copper.

[0015] Furthermore, the materials used for the electrodes are not particularly limited, but examples include tin, gold, silver, copper, 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 copper 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 above melting point is not particularly limited if the metal is solid at room temperature, but for example, it is preferably 150°C or higher. It is preferable that multiple protrusions are formed.

[0016] 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; 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). 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 protrusions. The size of substrate A (for example, wafer size) can be 100 mm or more in diameter (or the 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.

[0017] [Circuit board B] Circuit board B has wiring terminals. The thickness of substrate B is preferably 0.1 to 5 mm, and more preferably 0.2 to 1 mm. Substrate B may be a wafer, or it may be a single-sided chip or a double-sided chip. In the joint obtained by the manufacturing method of the joint of the present invention, at least a portion of the wiring terminals is electrically joined to the protrusions on the substrate A described above.

[0018] The material used for substrate B is not particularly limited, but the same material as that used for substrate A is 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 terminals. The size of substrate B (e.g., wafer size) can be 100 mm or more in diameter (or maximum diameter if substrate B is not circular). For larger substrates, it is preferable that they be 200 mm or more, and more preferably 250 mm or more. There is no particular upper limit, but it is preferable that they be 2,000 mm or less.

[0019] <Filler-containing layer formation process> The present invention provides a method for manufacturing a bonded body, which includes a step of forming a filler-containing layer containing a binder and a filler on the surface of the substrate A having the protrusions (filler-containing layer formation step). The filler-containing layer is preferably formed to be in contact with the above-mentioned protrusions, and more preferably formed to fill the recesses between the protrusions. Furthermore, while the filler-containing layer only needs to be formed on at least a portion of the above-mentioned protrusions, a configuration in which it is formed on all of the above-mentioned protrusions is also one of the preferred embodiments of the present invention.

[0020] The step of forming the filler-containing layer preferably includes applying a resin composition containing at least one resin selected from the group consisting of a binder and a binder precursor, and a filler, onto the surface of the substrate A having the protrusions.

[0021] 〔binder〕 The binder contained in the filler-containing layer is preferably an insulating binder. In this invention, an insulating binder is defined as having a volume resistivity of 1 × 10⁻⁶ 15 This refers to materials with a volume resistivity of Ω·cm or greater, where the volume resistivity is 1 × 10⁻⁶. 16 A value of Ω·cm or greater is preferred. There is no particular upper limit, but for example, 1 × 10⁻⁶ 18 A value of Ω·cm or less is preferable. Furthermore, the dielectric breakdown voltage of the binder is preferably 1 kV / mm or higher, and more preferably 10 kV / mm or higher. There is no particular upper limit, but for example, it is preferably 1000 kV / mm or lower. In this specification, volume resistivity and dielectric breakdown voltage can be measured in accordance with JIS (Japanese Industrial Standards) C2151:2006 and JIS C2318:2007.

[0022] Examples of binders, though not particularly limited, include polyimides, polybenzoxazoles, polyamide-imides, 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. These may be used individually or in combination of two or more types. Among these, the filler-containing layer preferably contains polyimide, polybenzoxazole, or polyamideimide, and more preferably contains polyimide. Details of these resins will be described later as components included in the resin composition.

[0023] Furthermore, the binder contained in the filler-containing layer preferably contains polymerizable groups, more preferably radical polymerizable groups, even more preferably groups having ethylenically unsaturated bonds, and particularly preferably contains at least one group selected from the group consisting of vinyl groups, acrylic groups, and methacrylic groups. Having such a base in the binder can further improve the adhesion between substrate A and substrate B.

[0024] The binder content relative to the total mass of the filler-containing layer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit of the above content is not particularly limited, but for example, it can be 50% by mass or less. If the filler-containing layer contains two or more types of binders, it is preferable that their total amounts are within the above range.

[0025] [Filler] The filler-containing layer contains a filler. The filler preferably has thermal conductivity. The filler may be electrically insulating, semiconductor, or conductive. The degree of electrical insulation and conductivity is appropriately selected according to the design and purpose. For example, in the case of an electrically insulating filler, the lower limit of the volume resistivity of the filler is preferably 1.0×10 11 Ω·cm or more, more preferably 3.0×10 11 Ω·cm or more, and particularly preferably 1.0×10 12 Ω·cm or more. The upper limit of the volume resistivity is not particularly limited, but for example, it is preferably 1.0×10 18 Ω·cm or less. On the other hand, in the case of a semiconductor or conductive filler, the lower limit of the volume resistivity of the filler is not particularly limited, but practically it is 1.0×10 -7 Ω·cm or more. The upper limit of the volume resistivity is preferably less than 1.0×10 11 Ω·cm.

[0026] The thermal diffusivity of the filler is, for example, preferably 5.0×10 -7 m 2 s -1 or more, more preferably 1.0×10 -6 m 2 s -1 or more, still more preferably 2.0×10 -6 m 2 s -1 or more, and particularly preferably 3.0×10 -6 m 2 s -1 or more. The upper limit of the thermal diffusivity of the filler is not particularly limited, but for example, it is preferably 1.0×10 -4 m 2 s -1 or less.

[0027] The density of the filler is, for example, preferably 4.0 g / cm 3 or less, more preferably 3.0 g / cm 3The 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.

[0028] 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.

[0029] 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, flaky, nanotube-shaped, etc., and any of these can be used. Furthermore, the IX-3 series and other products manufactured by Nippon Shokubai can also be suitably used.

[0030] 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.

[0031] 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.

[0032] These fillers can be used individually or in combination of two or more types. 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.

[0033] 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.

[0034] 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 filler-containing layer 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.

[0035] 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. Furthermore, the filler may be a mixture containing particles with a relatively small aspect ratio, such as spherical, plate-shaped, curved plate-shaped, or flaky particles, and particles with a relatively large aspect ratio, such as fibrous, rod-shaped, tubular, or needle-shaped particles. In this configuration, it may be possible to significantly improve thermal diffusivity.

[0036] 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.

[0037] The filler content in the filler-containing layer is preferably 1% by volume or more, more preferably 10% by volume or more, particularly preferably 20% by volume or more, and most preferably 50% by volume or more, relative to the volume of the filler-containing layer. Furthermore, from the viewpoint of improving the adhesion between substrate A and substrate B, it is more preferable that the filler-containing layer be 85% by volume or less, even more preferable that it be 81% by volume or less, and most preferable that it be 75% by volume or less. Furthermore, the filler content in the filler-containing layer is preferably 10% by mass or more, and more preferably 30% by mass or more, relative to the total mass of the filler-containing layer. 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.

[0038] 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.

[0039] 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.

[0040] [Other ingredients] The filler-containing layer may also contain other components. Other components include binders and their precursors, as well as components other than fillers, which are included in the resin composition described later.

[0041] [Method for forming a filler-containing layer] The step of forming the filler-containing layer preferably includes applying a resin composition containing at least one resin selected from the group consisting of a binder and a binder precursor, and a filler, onto the surface of the substrate A having the protrusions. Furthermore, the filler-containing layer is preferably a layer obtained by curing the above-mentioned resin composition.

[0042] -Resin composition- The binder contained in the resin composition is synonymous with the binder contained in the filler-containing layer described above, and the preferred embodiment is the same. The binder precursors contained in the resin composition refer to compounds that become the binders described above by heating or other operations as described later, and include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors as described later. Examples of fillers included in the resin composition include the fillers included in the filler-containing layer described above. Further details regarding the resin composition will be described later.

[0043] -How to apply- Examples of methods for applying a resin composition onto a substrate include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating.

[0044] Furthermore, if the resin composition contains a solvent, the process may include a step of drying the layer made of the resin composition after applying it to the substrate (drying step). The drying temperature of the film 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.

[0045] 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 filler-containing layer is as described below.

[0046] Furthermore, in the filler-containing layer formation process, the filler-containing layer may be formed not only on substrate A but also on substrate B (preferably on the surface of substrate B having the wiring terminals). The method for forming the filler-containing layer on substrate B is not particularly limited, but for example, a method similar to the method for forming the filler-containing layer on substrate A can be used. In other words, the step of forming a filler-containing layer on substrate B preferably includes applying a resin composition containing at least one resin selected from the group consisting of a binder and a binder precursor, and a filler, onto the surface of substrate B having the wiring terminals. In this case, it is preferable that the filler-containing layer on substrate A and the filler-containing layer on substrate B are bonded together. In this case, it is also preferable that the filler-containing layer on substrate B is planarized by a planarization process described later. The planarization method is the same as the method for planarizing the filler-containing layer on substrate A.

[0047] The filler-containing layer formation step may include a step of patterning a layer made of a resin composition. If the resin composition contains a photosensitive compound such as a photopolymerization initiator described later, this patterning can be carried out by exposure and development. After the filler-containing layer is formed, its surface is planarized. Details of the planarization process will be described later. Note that 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.

[0048] -Exposure process- The manufacturing method of the present invention may include an exposure step in which a layer made of a resin composition is exposed to light. The exposure amount is not particularly defined as long as the layer made of the resin composition is photosensitive, but for example, it may be 100 to 10000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. 2Irradiation is preferred, at a dose of 200-8000 mJ / cm². 2 Irradiation is more preferable. The exposure wavelength can be appropriately determined within the range of 190 to 1000 nm, with 240 to 550 nm being preferred. In relation to the light source, the exposure wavelengths include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 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 light; EUV (wavelength 13.6nm), and (6) electron beams. For layers made from 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 yield particularly high exposure sensitivity.

[0049] -Developing process- The manufacturing method of the present invention may include a developing step in which a layer made of an exposed resin composition is subjected to a developing treatment. By developing, the unexposed parts (non-exposed areas) or exposed parts (exposed areas) are removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as paddle, spray, immersion, and ultrasonic can be used. Development is performed using a developing solution. The developing solution can be used without particular limitations as long as the unexposed parts (non-exposed areas) or exposed parts (exposed areas) are removed. The developing solution preferably contains an organic solvent. The development time is preferably 10 seconds to 5 minutes. While there is no specific temperature requirement for development, it is usually carried out at 20 to 40°C. After processing with the developer, rinsing may be performed. Rinsing is preferably done with a solvent different from the developer. For example, rinsing can be done using a solvent contained in the resin composition. The rinsing time is preferably 5 seconds to 1 minute.

[0050] -Heating process- The filler-containing layer formation step described above may also preferably include heating the composition to a temperature of 150 to 300°C (heating step) after the above application. The above heating process can, for example, convert a binder precursor into a binder (for example, a cyclized resin precursor undergoes ring closure to become a cyclized resin), or promote polymerization between polymerizable compounds, or between polymerizable compounds and a binder. In this invention, the heating process in which the filler-containing layer is formed is also referred to as "additional baking." The heating temperature (maximum heating temperature) in the heating process is preferably 150 to 300°C, more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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 decomposition of the resin. 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.

[0056] [Physical properties of the filler-containing layer] The thickness of the filler-containing layer is not particularly limited, but from the viewpoint of exhibiting the effects of its physical properties, it is preferably 100 nm or more, more preferably 300 nm or more, even more preferably 500 nm or more, even more preferably 1 μm or more, and even more preferably 2 μm or more, in the state immediately before the planarization process described later. There is no particular upper limit, but it is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be measured using a known film thickness measuring device.

[0057] The thermal diffusivity of the filler-containing layer in the bonded structure described later is 2.0 × 10⁻⁶. -7 m 2 s -1 Preferably, it should be 3.0 × 10 -7 m 2 s -1 It is more preferable that the above be the case, 5.0 × 10 -7 m 2 s -1 It is even more preferable that the above conditions are met. The thermal diffusivity of the filler-containing layer can be adjusted by designing, for example, the type of filler material, the particle size of the filler (or the combination of particle sizes if two or more types of fillers are included), the thermal diffusivity of the filler, the filler content, the type of binder material, the thermal diffusivity of the binder, and the binder content.

[0058] The filler-containing layer is preferably an insulating layer. The insulating properties (electrical resistance) of the filler-containing layer are not particularly limited, but the volume resistivity is 1 × 10⁻⁶. 15 It is preferable that it be Ω·cm or more, 1 × 10 16 It is more preferable that it be greater than Ω·cm. There is no particular upper limit, but 1 × 10 19It is practical for the volumetric efficiency 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 volumetric efficiency and dielectric breakdown voltage shall conform to JIS C2151:2006 and JIS C2318:2007.

[0059] <Laminate Manufacturing Process> The present invention provides a method for manufacturing a bonded body, which includes a step of flattening the filler-containing layer together with the protrusions to expose at least a portion of the protrusions from the filler-containing layer and obtain a laminate (laminated body manufacturing step). The above-described laminate has a filler-containing layer laminated on a substrate A having a protrusion, and the protrusion is exposed on a part of the exposed surface of the filler-containing layer.

[0060] The planarization described above is preferably carried out by a process including cutting, mechanical polishing, chemical polishing, grinding, plasma treatment, or laser ablation, and more preferably by cutting. Alternatively, these methods can be combined, such as performing chemical polishing after cutting. Specifically, one example is to cut the surface of the filler-containing layer with a diamond cutting tool to expose a new surface of the filler-containing layer and the protrusions. By performing a planarization process on the substrate A, both the protrusions and the filler-containing layer, so that the protrusions are exposed, it becomes possible to expose the protrusions by simultaneously planarizing the protrusions and the filler-containing layer. Surface planarization can be performed, for example, using a surface planer. Examples of surface planars include those with a diamond cutting tool mounted on a spindle, such as the DISCO DFS8910, DFS8960, DAS8920, and DAS8930 (all are trade names). Another surface planarization method is chemical mechanical polishing (CMP).

[0061] [TTV] In the laminate manufacturing process, the filler-containing layer is flattened together with the protrusions. The degree of flattening is preferably such that the TTV (Total Thickness Variation) of the filler-containing layer and protrusions in the laminate 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 following steps are performed: dividing the area 1 mm or more inward from the edge of the filler-containing layer into 2 mm square sections (if the area of ​​the filler-containing layer is too small to be divided into 2 mm square sections, the entire area 1 mm or more inward from the edge of the filler-containing layer is considered one section); measuring the maximum thickness (T1) and minimum thickness (T2) between one surface and the other for each section; calculating the film thickness difference (T1-T2) for each section; assigning a ranking to the sections in descending order of film thickness difference (T1-T2); excluding a group of sections corresponding to 10% of the total number of sections (rounded down if decimal places exist) in descending order of film thickness difference, starting with the highest-ranking section (largest film thickness difference); and excluding a group of sections corresponding to 10% of the total number of sections (rounded down if decimal places exist), starting with the lowest-ranking section (smallest film thickness difference). In this specification, the term "partition evaluation TTV" may be used when referring specifically to the TTV of the filler-containing layer in the laminate as defined herein. Details of other measurement methods shall be as shown in the examples below. By keeping the TTV of the filler-containing layer in the laminate below the above upper limit, the film thickness becomes generally uniform, and the adhesion to the substrate B is improved.

[0062] [Ra] The filler-containing layer 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 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. The surface roughness (Ra) of the filler-containing layer of the present invention shall be determined by the measurement method shown in the examples below. By setting the surface roughness of the filler-containing layer to above the above lower limit, an anchoring effect can be activated to improve adhesion to the substrate. 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.

[0063] <Joining process> The method for manufacturing the bonded body of the present invention includes a step of joining the surface of the laminate having a filler-containing layer to the substrate B. Through bonding, the protrusions on substrate A and the wiring terminals on substrate B are electrically connected. The joining is preferably carried out by means including at least one of heating and pressurizing, 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 350°C or lower, even more preferably 300°C or lower, even more preferably 280°C or lower, even more preferably 260°C or lower, and even more preferably 250°C or lower. As mentioned above, 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. The manufacturing method of the bonded body of the present invention is effective in that it can reduce manufacturing costs by lowering this bonding temperature and can avoid damaging each component of the element. The heating time in the joining process is not particularly limited, but is preferably 30 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 filler-containing layer. 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 -4 It 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.

[0064] <Other processes> Furthermore, the method for manufacturing the bonded body of the present invention does not preclude the inclusion of other processes between the processes specified above. While the description has primarily focused on an example where substrate A and substrate B are joined face to face, 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 considerable thickness are placed side-by-side and their sides are joined together is also possible.

[0065] <Example of a manufacturing method for a joined 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 3 and conductive passages 31 (protrusions 30) 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.

[0066] A resin composition is applied to the electrode-laid surface (the surface having the electronic circuit region) P0 of the substrate A1 to form a layer (resin composition layer) 4 made of the resin composition (Figure 2(b)). In this embodiment, a polyimide precursor is used as an example for the resin composition layer. In this state, the resin composition layer may be heated and dried (drying step). Alternatively, after pre-baking, the resin composition layer 4 may be patterned by photolithography or ion sputtering.

[0067] Subsequently, in this embodiment, the polymer precursor is crosslinked by irradiation with ultraviolet light and then heated (heating step 2) to promote cyclization and harden the filler-containing layer 41 (Figure 2(c)). This forms a filler-containing layer-distributed substrate 1y on substrate A1 with the filler-containing layer 41 disposed thereon. As in this example, the filler-containing layer 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, patterning may be performed before hardening, and guide channels may be created in the patterned areas by plating or other means.

[0068] In the filler-containing layer substrate 1y of this embodiment, the heights h1 and h2 of the guide channels 31 vary. Also, the surface 4a of the filler-containing layer is wavy and not flat. In this embodiment, planarization is performed to eliminate the variations in the height of the guide channels 31, expose their leading surface, and flatten the surface of the filler-containing layer.

[0069] Figure 3 shows the filler-containing layer substrate (laminated structure) 1z after planarization. The tip 31a of the guide channel 31 is exposed on the surface 4b of this filler-containing layer, and the entire surface 4b of the filler-containing layer is planarized.

[0070] A substrate B is prepared separately for the laminate (a planarized filler-containing layer 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 arranged thereon, and electrodes 32 formed within the circuit wiring region 8. At this time, the laminate is aligned so that the portion of the conductive path 31 and the electrodes 32 provided on substrate B2 coincide.

[0071] Next, in this embodiment, the aligned substrate B2 and the laminate 1z are joined by contacting them at the bonding surface P1 via the filler-containing layer 41 (Figure 4(b)). This forms a bonded body 100 in which two substrates are joined together. In this state, by performing a heat treatment (reflow), the guide passage 31 is melted, and the electrode 3 on substrate A and the electrode 32 on substrate B can be electrically connected via the guide passage 31 (bonding process). Simultaneously, the filler-containing layer 41 is softened by the heating described above, and the surface 4b of the filler-containing layer of the laminate 1z is bonded to the surface 2a of the substrate B (the surface having the electronic circuit region), thereby forming the bonded body 100. This allows for an electrical connection between substrate A and substrate B, as well as a secure and stable fixation between them. In this specification, the electrode 3 and the guide passage 31 may be collectively referred to as the protrusion 30. The electrode 32 on the substrate B may be referred to as the pad.

[0072] In a preferred embodiment of the present invention, the filler-containing layer 41 has excellent thermal conductivity because it contains fillers. Therefore, heat generated from, for example, the electronic circuit region 8 can be dissipated through the filler-containing layer 41. Furthermore, in a preferred embodiment of the present invention, the flatness of the filler-containing layer surface P1 of the laminate 1z is high, which allows for a dense and precise contact state with the substrate B2 at the contact surface. By achieving a denser and more precise contact state, voids that tend to occur at the contact surface can be effectively suppressed.

[0073] (Manufacturing methods for semiconductor devices) The semiconductor device of the present invention comprises a bond obtained by the method for manufacturing a bond of the present invention. Examples of semiconductor devices include those described in "Illustrated Guide to All About Cutting-Edge Semiconductor Packaging Technology" edited by the Semiconductor New Technology Research Group, published by 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, published by Kogyo Chosakai, pp. 32-41, 56-59. Specifically, examples include using the above-mentioned filler-containing layer as an adhesive film to replace the underfill between chips, and using the above-mentioned filler-containing layer as a die bonding film to fix the chips. Furthermore, the manufacturing method of the bonded structure 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 method for manufacturing the bonded structure of the present invention can be suitably used for three-dimensional mounting 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 the filler-containing layer described above. A surface electrode 120a is provided on one side of the wiring substrate 120. An insulating layer 115 with a rewiring layer 105 formed on it is placed 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 surface of the semiconductor element 101d on the side of 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 manufacturing method of the joint of the present invention can also be used to join this insulating layer 115 and the laminate 101. That is, for example, the resin layer 110a can be the filler-containing layer described above. A resin layer 110b is formed between the insulating layer 115 and the wiring board 120. The manufacturing method of the joint of the present invention can also be used to join this insulating layer 115 and the wiring board 120. In other words, for example, the resin layer 110b can be the filler-containing layer described above.

[0074] (Resin composition) The resin composition of the present invention is a resin composition used for forming the filler-containing layer in the method for manufacturing the bonded body of the present invention. The following describes in detail the resin composition used to form the filler-containing layer in the method for manufacturing the bonded body of the present invention (i.e., the resin composition of the present invention).

[0075] The resin composition of the present invention comprises at least one resin selected from the group consisting of binders and binder precursors, and a filler. The filler is as described above in the resin composition of the present invention. However, the phrase "relative to the total mass of the filler-containing layer" shall be read as "relative to the total solid content of the resin composition."

[0076] Examples of binders include the following cyclized resins or their precursors, or other resins, but it is preferable to include at least one resin selected from the group consisting of cyclized resins and their precursors (hereinafter also referred to as "specific resin"), and it is more preferable to include a precursor of a cyclized resin.

[0077] <Specific resin> The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. In this invention, the main chain refers to the relatively longest bonding chain within the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as the specific resin. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin. Further, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described below, more preferably contains the radical polymerization initiator described below and a radical crosslinking agent described below. Furthermore, if necessary, a sensitizer described below can be contained. From such a resin composition of the present invention, for example, a negative-type photosensitive film is formed. In addition, the specific resin may have a polarity-converting group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described below. From such a resin composition of the present invention, for example, a positive-type photosensitive film or a negative-type photosensitive film which is chemically amplified is formed.

[0078] 〔Polyimide Precursor〕 The polyimide precursor used in the present invention is not particularly limited in terms of its type or the like, but preferably contains a repeating unit represented by the following formula (2).

Chemical Formula

[0079] A in formula (2) 1and A 2 each independently represents an oxygen atom or -NH-, and an oxygen atom is preferred. R in formula (2) 111 represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The above linear or branched aliphatic group may be substituted with a group in which a hydrocarbon group in the chain contains a heteroatom, and the above cyclic aliphatic group and aromatic group may be substituted with a group in which a hydrocarbon group of the ring member contains a heteroatom. As a preferred embodiment of the present invention, a group represented by -Ar- and -Ar-L-Ar- is exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. However, Ar is each independently an aromatic group, and L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group composed of a combination of two or more of the above. These preferred ranges are as described above.

[0080] R 111 is preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds may be used. Specifically, it 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 group composed of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The above linear or branched aliphatic group may be substituted with a group in which a hydrocarbon group in the chain contains a heteroatom, and the above cyclic aliphatic group and aromatic group may be substituted with a group in which a hydrocarbon group of the ring member contains a heteroatom. Examples of the group containing an aromatic group include the following.

[0081] [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.

[0082] 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.

[0083] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0084] 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.

[0085] 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.

[0086] Also, R 111From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0087] R in equation (2) 115 represents a tetravalent organic group. Preferably, the tetravalent organic group is one containing an aromatic ring, and more preferably, a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * each independently represents a bonding site with another structure.

Chemical formula

[0088] R 115 Specific examples include tetracarboxylic acid residues remaining after removal of the anhydride group from a tetracarboxylic dianhydride. The polyimide precursor may contain only one type or two or more types of structures corresponding to R 115 as tetracarboxylic dianhydride residues. The tetracarboxylic dianhydride is preferably represented by the following formula (O).

Chemical formula

[0089] 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.

[0090] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0091] 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.

[0092] 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.

[0093] [ka]

[0094] 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 viewpoints of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups. More preferably, it is a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably, it is a polyethyleneoxy group. In the group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged, may form blocks and be arranged, or may be arranged in an alternating pattern or the like. Preferred embodiments of the repeating number of ethyleneoxy groups and the like in these groups are as described above.

[0095] In formula (2), R 113 is a hydrogen atom, or R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenic unsaturated bond. Examples of such a tertiary amine compound having an ethylenic unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0096] In formula (2), R 113 and R 114 at least one of may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0097] Also, it is preferable that the polyimide precursor 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.

[0098] 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, as the diamine, embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be mentioned.

[0099] 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 kind of the polyimide precursor 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

[0100] A 1 、A 2 、R 111 、R 113 and R <00001​​​​​​113 and R 114 This is synonymous with the same thing, and the preferred range is also similar. R 112 R in equation (5) is 112 This is synonymous with the same thing, and the preferred range is also similar.

[0101] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). 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).

[0102] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more 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).

[0103] 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.

[0104] [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.

[0105] -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.

[0106] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 131 It is more preferable that it be included as an organically modified (poly)siloxane structure, as described later. Furthermore, the silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0107] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has ethylenically unsaturated bonds. Polyimides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is 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 a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later.131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0108] [ka]

[0109] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0110] In formula (IV), R 21 This represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination thereof. Of the alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0111] Among these, R 21 It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1). [ka] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). 21 This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxy group having 2 to 30 carbon atoms in L are as described above for R 21 This is similar to the preferred embodiment of the alkylene group having 2 to 12 carbon atoms, or the (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In equations (R1) to (R3), * is equivalent to * in equation (IV), and the same applies to the preferred embodiment. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0112] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0113] 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.

[0114] -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.

[0115] -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.

[0116] - 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.

[0117] -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.

[0118] 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).

[0119] 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:

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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 the residue is an aromatic diamine residue having 1 to 4 aromatic rings.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] -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

[0129] 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).

[0130] 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.

[0131] 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.

[0132] [Polybenzoxazole precursor] The polybenzoxazole precursor used in this invention does not have any particular structure, but preferably contains repeating units represented by the following formula (3). [ka] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0133] In equation (3), R 123 and R 124 These are R in equation (2), respectively. 113 This is synonymous with the same, and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group. In equation (3), R 121 R represents a divalent organic group. A divalent organic group is preferably one containing at least one of an aliphatic group and an aromatic group. A linear aliphatic group is preferred. 121 A dicarboxylic acid residue is preferred. One or more dicarboxylic acid residues may be used.

[0134] As the dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, and dicarboxylic acid residues containing an aromatic group are more preferred. As for dicarboxylic acids containing an aliphatic group, dicarboxylic acids containing a linear or branched (preferably linear) aliphatic group are preferred, and dicarboxylic acids consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. Examples include suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formula.

[0135] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0136] As for dicarboxylic acids containing aromatic groups, dicarboxylic acids having the following aromatic groups are preferred, and dicarboxylic acids consisting only of the following aromatic groups and two -COOH groups are more preferred.

[0137] [ka] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-, and * represents a binding site with another structure, independently.

[0138] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0139] In equation (3), R 122 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) above is 115 This is synonymous with the same thing, and the preferred range is also similar. R 122It is also preferable that the group is derived from a bisaminophenol derivative, and examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(4-amino Examples include bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used individually or in combination.

[0140] Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

[0141] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Also, R 122 It is also preferable that the structure be represented by the above formula. 122However, if the structure is represented by the above formula, then of the four * and # characters, any two of them are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the other two are R in formula (3). 122 It is preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 Either the bond site with the nitrogen atom to which it is bonded, or the two *s are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the two #s are R in formula (3). 122 It is more preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 It is even more preferable that the site is a bonding site with the nitrogen atom to which it is bonded.

[0142] The bisaminophenol derivative is also preferably a compound represented by formula (As). [ka]

[0143] In formula (As), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of formulas (A-sc) below. R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

[0144] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

[0145] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, is considered to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, and is particularly preferable because it further enhances the effect of high cyclization rate when cured at low temperatures.

[0146] Furthermore, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, as this maintains the effects of high transparency to i-lines and a high cyclization rate when cured at low temperatures.

[0147] Furthermore, it is even more preferable that R1 in the above formula (As) is an alkylene or a substituted alkylene. Specific examples of alkylenes and substituted alkylenes for R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferable because they allow for the production of a well-balanced polybenzoxazole precursor that maintains high transparency to i-lines and a high cyclization rate when cured at low temperatures, while also having sufficient solubility in solvents.

[0148] For a method of producing the bisaminophenol derivative represented by the above formula (As), refer to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference.

[0149] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated herein by reference. Of course, it goes without saying that we are not limited to these.

[0150] The polybenzoxazole precursor may include other types of repeating units in addition to the repeating unit of formula (3) above. The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that it can suppress the occurrence of warping associated with ring closure.

[0151] [ka] In formula (SL), Z has an a structure and a b structure, and R 1s R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 2s R is a hydrocarbon group having 1 to 10 carbon atoms. 3s , R 4s , R 5s , R 6s At least one of the groups is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of structures a and b may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol% for structure a, 95 to 5 mol% for structure b, and 100 mol% for a + b.

[0152] In formula (SL), preferred Z is R in the b structure. 5s and R 6s Examples include those in which the group is a phenyl group. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, thereby achieving both the effect of suppressing warping and the effect of improving solvent solubility.

[0153] When other types of repeating units include diamine residues represented by formula (SL), it is also preferable to include tetracarboxylic acid residues remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as repeating units. An example of such tetracarboxylic acid residues is R in formula (2). 115 Examples include:

[0154] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The degree of molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole precursor, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole 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 polybenzoxazole precursors are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polybenzoxazole precursors as a single resin are, respectively, within the above range.

[0155] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) that has a polymerizable group. A radical polymerizable group is preferred as the polymerizable group. Alternatively, it may be a compound represented by the following formula (X) that has a polarity conversion group such as an acid-degradable group. [ka] In formula (X), R 133 represents a divalent organic group, R 134 This represents a tetravalent organic group. If it has a polarity-converting group such as a polymerizable group or an acid-degradable group, the polarity-converting group such as a polymerizable group or an acid-degradable group is R 133 and R 134 It may be located at least one of the two, or it may be located at the terminal end of the polybenzoxazole as shown in formula (X-1) or formula (X-2) below. Formula (X-1) [ka] In formula (X-1), R 135 and R 136 At least one of the groups is a polarity-converting group such as a polymerizable group or an acid-degradable group; if it is not a polarity-converting group such as a polymerizable group or an acid-degradable group, it is an organic group; and the other group is equivalent to formula (X). Formula (X-2) [ka] In formula (X-2), R 137 is a polarity-converting group such as a polymerizable group or an acid-degradable group, the others are substituents, and the other groups are synonymous with formula (X).

[0156] Polarity-converting groups such as polymerizable groups or acid-degradable groups are synonymous with the polymerizable groups described above in relation to the polymerizable groups of the polyimide precursor.

[0157] R 133 R represents a divalent organic group. Examples of divalent organic groups include aliphatic groups and aromatic groups. A specific example is R in formula (3) of the polybenzoxazole precursor. 121 Examples include R. 121 It is similar to that.

[0158] R 134 R represents a tetravalent organic group. An example of a tetravalent organic group is R in formula (3) of the polybenzoxazole precursor. 122 Examples include R. 122 It is similar to that. For example, R 122The four bonders of the tetravalent organic group, as exemplified above, bond with the nitrogen and oxygen atoms in formula (X) to form a fused ring. For example, R 134 However, if it is the following organic group, it forms the following structure. In the following structure, * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively. [ka]

[0159] The polybenzoxazole preferably has an oxazole conversion rate of 85% or more, and more preferably 90% or more. There is no particular upper limit, and it may be 100%. By having an oxazole conversion rate of 85% or more, the membrane shrinkage due to ring closure that occurs when oxazole is converted by heating is reduced, and the occurrence of warping can be suppressed more effectively. The above oxazole conversion rate can be measured, for example, by the following method. The infrared absorption spectrum of polybenzoxazole was measured, and the absorption peak at 1650 cm², which originates from the amide structure of the precursor, was observed. -1 Determine the peak intensity Q1 in the vicinity. Next, 1490 cm -1 The absorption intensity of aromatic rings found nearby is used for normalization. After heat treatment of the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the spectroscopy is performed at 1650 cm⁻¹. -1 The peak intensity Q2 in the vicinity was calculated to be 1490 cm. -1 The absorption intensity of the aromatic rings observed nearby is used for normalization. Using the normalized peak intensities Q1 and Q2 obtained, the oxazole rate of polybenzoxazole can be determined based on the following formula. Oxazole conversion rate (%) = (Specific value of peak intensity Q1 / Specific value of peak intensity Q2) × 100

[0160] Polybenzoxazoles are all of the same type R 131 or R 132 The repeating unit of the above formula (X) may include two or more different types of R 131 or R 132The polybenzoxazole may contain repeating units of the above formula (X), including the above formula (X). In addition, the polybenzoxazole may contain other types of repeating units besides the repeating units of the above formula (X).

[0161] Polybenzoxazoles are, for example, bisaminophenol derivatives and R 133 It is obtained by reacting a dicarboxylic acid containing or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, and then oxazoleizing this using a known oxazole reaction method. In the case of dicarboxylic acids, to increase the reaction yield, etc., an activated ester-type dicarboxylic acid derivative that has been pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used.

[0162] The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more types of polybenzoxazole are contained, it is preferable that the weight-average molecular weight of at least one of the polybenzoxazoles is within the above range. Furthermore, the number-average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The degree of molecular weight dispersion of the polybenzoxazole is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole 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 polybenzoxazoles are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polybenzoxazole are treated as a single resin are, respectively, within the above range.

[0163] [Polyamide-imide precursors] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 represents a hydrogen atom or a monovalent organic group.

[0164] In formula (PAI-2), R 117 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0165] Also, R 117 It is preferable that it be derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. Chlorination is preferred as the halogenation. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the above tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used individually or in combination of two or more.

[0166] Specifically, preferred tricarboxylic acid compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0167] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene group. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group has been converted to a halogen (e.g., trimellitic anhydride chloride).

[0168] In formula (PAI-2), R 111 , A 2 , R 113 These are the R values ​​in equation (2) above. 111 , A 2 , R 113 This is synonymous with the same as the preferred configuration.

[0169] The polyamide-imide precursor may further contain other repeating units. Other repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below. [ka]

[0170] In formula (PAI-1), R 116 represents a divalent organic group, R111 This represents a divalent organic group. In formula (PAI-1), R 116 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0171] Also, R 116It is preferable that it be derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl group in a dicarboxylic acid dihalide compound may be halogenated, but it is preferable that it is chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used individually or in combination of two or more.

[0172] Specifically, preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0173] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebaic acid, and hexadeca. Examples include fluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalide compounds include compounds in which the two carboxyl groups in the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

[0174] In formula (PAI-1), R 111 R in equation (2) above is 111 This is synonymous with the same as the preferred configuration.

[0175] Furthermore, the polyamide-imide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0176] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine component.

[0177] One embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and 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 polyamideimide precursor, excluding the terminals, may be any of the repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2). Another embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) 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 polyamideimide precursor, excluding the terminals, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0178] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of dispersion of the molecular weight of the polyamide-imide 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 for the degree of dispersion of the molecular weight of the polyamide-imide 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. Furthermore, if the resin composition contains multiple types of polyamide-imide 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 polyamide-imide 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 when the multiple types of polyamide-imide precursors are treated as a single resin are, respectively, within the above ranges.

[0179] [Polyamide-imide] The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide, or a polyamide-imide that is soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyamide-imide refers to a polyamide-imide 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 polyamide-imide 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 polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures in its main chain.

[0180] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyamide-imide contains fluorine atoms. Fluorine atoms, for example, are R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later.117 , or R 111 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0181] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyamide-imide may have ethylenically unsaturated bonds. Polyamide-imides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later. 117 , or R 111 It is more preferable that it be included as a group having an ethylenically unsaturated bond. A preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the polyimide described above.

[0182] The amount of ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0183] -Polymerizable groups other than ethylenically unsaturated bonds- Polyamide-imides may have polymerizable groups other than ethylenically unsaturated bonds. Polymerizable groups other than ethylenically unsaturated bonds in polyamide-imides include the same groups as those described above for polymerizable groups other than ethylenically unsaturated bonds in polyimides. Polymerizable groups other than ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (PAI-3) described later.111 It is preferable that it be included in The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0184] -Polar Conversion Group- Polyamide-imides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyamide-imides 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.

[0185] - Acid Value - When polyamide-imide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamide-imide 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 polyamide-imide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamide-imide is preferably 2 to 35 mg KOH / g, more preferably 3 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, examples of acid groups contained in polyamideimides include the same groups as those in the polyimides described above, and the preferred embodiments are also the same.

[0186] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyamide-imide has a phenolic hydroxyl group. Polyamide-imides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. Phenolic hydroxyl groups are, for example, R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0187] The polyamide-imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). [ka] In formula (PAI-3), R 111 and R 117 These are R in equation (PAI-2), respectively. 111 and R 117 This is synonymous with the same as the preferred configuration. If it has polymerizable groups, the polymerizable groups are R 111 and R 117 It may be located at least one of the two or at the end of the polyamide-imide.

[0188] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to encapsulate the main chain ends of the polyamide-imide with an end-capturing agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. The preferred embodiment of the end-capturing agent is the same as the preferred embodiment of the end-capturing agent in polyimide described above.

[0189] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of polyamide-imide 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 is measured by the same method as the ring closure rate of the polyimide described above.

[0190] Polyamide-imides are all of the same type R 111 or R 117 It may include the repeating unit represented by the above formula (PAI-3), and may contain two or more different types of R 131 or R 132 The polyamide-imide may also contain repeating units represented by the above formula (PAI-3). In addition to the repeating units represented by the above formula (PAI-3), the polyamide-imide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0191] Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method and then completely imidizing it using a known imidation reaction method, or by stopping the imidation reaction midway and introducing a partial imide structure, or by blending a fully imidized polymer with its polyamide-imide precursor to introduce a partial imide structure.

[0192] The weight-average molecular weight (Mw) of the polyamide-imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyamide-imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of molecular weight dispersion of the polyamide-imide 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 for the degree of molecular weight dispersion of the polyamide-imide, 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 polyamide-imides 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 polyamide-imides 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 polyamide-imides are treated as a single resin are, respectively, within the above ranges.

[0193] [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.

[0194] -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.

[0195] -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.

[0196] [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 mass of the resin composition excluding the filler from the total solid content. 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 mass of the resin composition excluding the filler from the total solid content. 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.

[0197] 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.

[0198] <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 limitations.

[0199] 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 mass of the resin composition excluding fillers from the total solids. 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 mass of the resin composition excluding the filler from the total solid content. 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 mass of the resin composition excluding fillers from the total solids. 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.

[0200] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0201] [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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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).

[0213] 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, based on the total mass of the resin composition of the present invention excluding fillers from the total solid content. 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.

[0218] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0219] [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.

[0220] 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.

[0221] [ka]

[0222] 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.

[0223] 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.

[0224] [ka]

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] [ka]

[0230] [ka]

[0231] 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.

[0232] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.).

[0237] 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.

[0238] - 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.

[0239] 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.

[0240] 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.

[0241] [ka]

[0242] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0243] 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.

[0244] -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.

[0245] -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.

[0246] 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.

[0247] 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 mass of the resin composition of the present invention excluding the filler from the total solid content. 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.

[0248] [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 thermal polymerization initiator.

[0249] -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.

[0250] 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.

[0251] 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 mass of the composition excluding fillers from the total solids. 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.

[0252] -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.

[0253] 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.

[0254] 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.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, whose convergence and maximum absorption wavelengths are matched to light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this is incorporated herein by reference.

[0260] 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.

[0261] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0262] 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.

[0263] 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.

[0264] 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.

[0265] [ka]

[0266] 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]

[0267] 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.

[0268] 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.

[0269] 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.

[0270] 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).

[0271] 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.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] [ka]

[0282] 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.

[0283] [ka]

[0284] In the formula, R I05 ~R I07 This is R in equation (I) above. I02 ~R I04 It is the same as this.

[0285] 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.

[0286] 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.

[0287] 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, based on the total mass of the resin composition of the present invention excluding fillers from the total solid content. 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.

[0288] [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.

[0289] 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 mass of the resin composition excluding fillers from the total solid content. The sensitizer may be used alone or in combination of two or more types.

[0290] [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.

[0291] 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.

[0292] 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 mass of the resin composition of the present invention excluding fillers from the total solid content. 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.

[0293] [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.

[0294] 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.

[0295] 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.

[0296] 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.

[0297] 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.

[0298] Furthermore, specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0299] 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.

[0300] 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.

[0301] 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.

[0302] [ka]

[0303] 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.

[0304] In equation (OS-1), m3 is 3, and X 3 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.

[0305] 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.

[0306] [ka]

[0307] 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.

[0308] 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.

[0309] 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.

[0310] 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]

[0311] In formula (OS-106) ~ formula (OS-111), R t1 R represents an alkyl group, an aryl group, or a heteroaryl group. t7 represents a hydrogen atom or a bromine atom, R 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.

[0312] 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.

[0313] 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.

[0314] 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).

[0315] [ka]

[0316] 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.

[0317] 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.

[0318] 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.).

[0319] Furthermore, compounds represented by the following structural formula are also preferred examples. [ka]

[0320] 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.

[0321] 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.

[0322] Examples of disulfone compounds include those described in Japanese Patent Publication No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

[0323] 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.

[0324] 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.

[0325] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0326] 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, based on the total mass of the resin composition excluding the filler from the total solid content. 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.

[0327] <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]

[0328] 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.

[0329] 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.

[0330] 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.

[0331] 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.

[0332] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2). [ka]

[0333] 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.

[0334] 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.

[0335] 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.

[0336] Compounds represented by formula (B1-1) are preferred, as are compounds represented by formula (B1-1a). [ka]

[0337] 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.

[0338] [ka]

[0339] 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.

[0340] 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]

[0341] 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.

[0342] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1). [ka]

[0343] 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.

[0344] 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.

[0345] 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.

[0346] 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.

[0347] 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.

[0348] R C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

[0349] 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.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

[0355] [ka]

[0356] 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.

[0357] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0358] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0359] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0360] 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.

[0361] <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.

[0362] 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.).

[0363] 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.

[0364] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0365] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0366] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0367] 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.

[0368] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0369] 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.

[0370] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0371] 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.

[0372] 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.

[0373] 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.

[0374] <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.

[0375] [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.

[0376] [ka]

[0377] 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.

[0378] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0379] 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.

[0380] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of resin. 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 is within the above range.

[0381] <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.

[0382] 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.

[0383] Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

[0384] 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.

[0385] Specific examples of migration inhibitors include the following compounds.

[0386] [ka]

[0387] 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 mass of the resin composition of the present invention excluding fillers from the total solid content.

[0388] 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.

[0389] <Polymerization inhibitors> 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.

[0390] 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.

[0391] 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 mass of the resin composition of the present invention excluding fillers from the total solid content.

[0392] 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.

[0393] <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.

[0394] 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.

[0395] 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.

[0396] 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 mass of the composition excluding fillers from the total solids.

[0397] 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.

[0398] <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.

[0399] [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.

[0400] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the efficiency of the liquid can be further improved. Specifically, when forming a film using a coating solution to which a surfactant-containing composition has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0401] 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]

[0402] 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.

[0403] 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.

[0404] 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,...

Claims

1. A step of preparing a substrate A having a surface with a protrusion, and a substrate B having wiring terminals. A step of forming a filler-containing layer containing a binder and a filler on the surface of the substrate A having the protrusions, The steps include: flattening the filler-containing layer together with the protrusions to expose at least a portion of the protrusions from the filler-containing layer and obtaining a laminate; The process includes joining the surface of the laminate having the filler-containing layer to at least a portion of the wiring terminals of the substrate B, The filler includes a granular mixture in which at least two groups of particles with different particle sizes are mixed. A method for manufacturing a composite body.

2. The method for manufacturing a bonded body according to claim 1, wherein the step of forming the filler-containing layer includes applying a resin composition comprising at least one resin selected from the group consisting of a binder and a binder precursor, and a filler, onto the surface of the substrate A having the protrusions.

3. The method for producing a bonded body according to claim 2, wherein the step of forming the filler-containing layer includes heating the composition at a temperature of 150 to 300°C after application.

4. The method for producing a composite body according to claim 1, wherein the filler has multiple peaks in the particle size distribution of the filler, and the peak particle size ratio between at least two peaks is 1.5 to 50, or is a mixture containing spherical, plate-like, curved plate-like, or flaky particles and fibrous, rod-like, tubular, or needle-like particles.

5. The method for producing a bonded body according to claim 2, wherein the resin composition comprises at least one resin selected from the group consisting of cyclized resins and their precursors.

6. A method for manufacturing a bonded body according to any one of claims 1 to 4, wherein the TTV of the filler-containing layer in the laminate is 10 μm or less, and the TTV is defined as the arithmetic mean of the film thickness difference (T1-T2) of each section, obtained by dividing the region 1 mm or more inward from the edge of the filler-containing layer into 2 mm square sections, measuring the maximum thickness (T1) and the 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 each section in descending order of film thickness difference (T1-T2), excluding a number of section groups corresponding to 10% of the total number of sections in descending order of film thickness difference from the top section, and excluding a number of section groups corresponding to 10% of the total number of sections in descending order of film thickness difference from the bottom section, and the TTV is the arithmetic mean of each film thickness difference (T1-T2) of the remaining section groups.

7. A method for manufacturing a joint according to any one of claims 1 to 4, wherein the protrusion includes metal.

8. The method for manufacturing a bonded body according to claim 7, wherein the metal comprises at least one metal selected from the group consisting of copper, tin, and nickel.

9. The method for manufacturing a bonded body according to any one of claims 1 to 4, wherein the protrusion comprises at least a layer containing copper and a layer containing tin.

10. A method for manufacturing a bonded body according to any one of claims 1 to 4, wherein the binder contained in the filler-containing layer is an insulating binder.

11. A method for producing a bonded body according to any one of claims 1 to 4, wherein the binder contained in the filler-containing layer contains at least one group selected from the group consisting of vinyl groups, acrylic groups, and methacrylic groups.

12. A method for producing a bond according to any one of claims 1 to 4, wherein the binder contained in the filler-containing layer comprises polyimide, polybenzoxazole, or polyamideimide.

13. A method for producing a bonded body according to any one of claims 1 to 4, wherein the filler comprises at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide.

14. The volume resistivity of the filler is 1.0 x 10 １１ A method for manufacturing a bond according to any one of claims 1 to 4, wherein the bond is Ω·cm or larger.

15. The method for manufacturing a composite body according to any one of claims 1 to 4, wherein the average particle diameter of the filler is 10 μm or less, and the average particle diameter is the average value of the diameter of the minimum inclusion circle relative to the apparent contour of each particle.

16. A method for manufacturing a bonded body according to any one of claims 1 to 4, wherein the planarization in the step of obtaining the laminated body is performed by cutting.

17. A method for manufacturing a joined body according to any one of claims 1 to 4, wherein the joining temperature in the joining step is 300°C or less.

18. The thermal diffusivity of the filler-containing layer in the resulting bonded structure is 2.0 × 10⁻⁶. －７ I understand ２ s －１ The method for manufacturing a jointed body according to any one of claims 1 to 4.

19. A method for manufacturing a semiconductor device, comprising a bond obtained by the method for manufacturing a bond according to any one of claims 1 to 4.

20. A resin composition used for forming the filler-containing layer in the method for manufacturing a bonded body according to any one of claims 1 to 4.

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