Methods for manufacturing compositions containing polyimide portions, methods for manufacturing conjugates, methods for manufacturing conjugates and devices, and devices.

Abstract

This invention provides a composition for forming a polyimide portion, a method for manufacturing a bond using the aforementioned composition for forming a polyimide portion, a method for manufacturing a bond, and a device. The aforementioned composition for forming a polyimide portion is used in a method for manufacturing a bond comprising the following steps: a step of preparing a substrate A; a step of forming a polyimide portion on a surface of the substrate A having wiring terminals; a step of preparing a substrate B; and a bonding step of bonding the surface of the substrate A having the polyimide portion to the surface of the substrate B having wiring terminals, wherein the polyimide portion is a component formed by the aforementioned composition for forming a polyimide portion, and the glass transition temperature of the polyimide portion is lower than the bonding temperature in the bonding step.

Description

Technical Field

[0001] This invention relates to a composition for forming a polyimide portion, a method for manufacturing an adhesive, a method for manufacturing an adhesive, and an apparatus. Prior Technology

[0002] As electronic devices such as mobile phones and tablet computers become increasingly miniaturized, their functions also become more diversified. To meet this demand, the electronic circuits assembled into these devices require further miniaturization, high integration, and high-density mounting. As technologies that achieve multifunctionality while maintaining high performance and reliability and miniaturization, mounting technologies such as SIP (System in Package), MCM (Multi-Chip Module), and POP (Package on Package) have gained attention. These technologies can reduce the number of components and simplify semiconductor manufacturing processes, thus promising to reduce the cost of electronic devices.

[0003] In System-on-Pack (SIP), the chips are connected by wire bonding, making it difficult to achieve the same processing speed as conventional System-on-Chip (SoC). Furthermore, the wire bonding process is complex, and improvements in product cost and quality are desired. To address these issues, Chip-on-Chip (COC) mounting technology has been developed. In COC, flip-chip bonding connects the chips and shortens the transmission distance, achieving speed performance comparable to SoC. Figure 1 is a cross-sectional view showing the structure of a typical COC. In this example, the COC consists of a daughter chip (first substrate) 1 and a mother chip (second substrate) 2. Electronic circuitry (not shown) and flip-chip electrodes (not shown) are formed on the mother chip 2. The daughter chip 1 is supported and connected via solder electrodes (bumps) 93. The solder electrodes 93 are surrounded by underfill 94 to ensure insulation. The mother chip 2 is mounted on the substrate 98 while maintaining insulation by being attached to it by an adhesive film 91. Electrical connections are made via bonding pads 97b, bonding wires 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 in the semiconductor device 90, and the device is assembled into an electronic device via these solder balls. Furthermore, techniques for further application of this flip chip mounting were investigated, and a three-dimensional mounting technique using TSV (Through Silicon Via) and its materials were employed (Non-Patent Document 1).

[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

[0005] In a COC structure component as shown in Figure 1 above, after the sub-chip 1 and the mother chip 2 are connected and fixed with solder bumps 93, an underfill 94 is filled into the gap between them. Therefore, a fluid resin is used as the material constituting the underfill, and it is formed by hardening after being filled between the solder bumps. Here, the sub-wafer 1 and the mother wafer 2 are bonded together by the adhesion of the resin, but from the point of view of improving adhesion, it is necessary to increase the maximum peel resistance between the two substrates. Summary of the Invention

[0006] Therefore, the object of the present invention is to provide a polyimide-containing composition for forming a bond that can obtain a bond with a large maximum peel resistance between two substrates when bonding two substrates, a method for manufacturing a bond using the above-mentioned polyimide-containing composition, a bond obtained by the above-mentioned manufacturing method, a method for manufacturing a device including the above-mentioned bond manufacturing method, and a device including the above-mentioned bond.

[0007] The following are examples of specific embodiments of the present invention. <1> A composition containing a polyimide portion for forming, used in a method for manufacturing an assembly comprising the following steps: The step of preparing a substrate A with wiring terminals on the side; The step of forming a polyimide-containing portion on the surface of the substrate A having the wiring terminals described above; The step of preparing a substrate B having a side with wiring terminals; and The bonding step involves joining the surface of substrate A containing the polyimide portion to the surface of substrate B containing the wiring terminals, wherein... The aforementioned polyimide-containing portion is a component formed from the aforementioned polyimide-containing portion forming composition. The glass transfer temperature containing the polyimide portion is lower than the bonding temperature in the bonding step described above. <2> like <1> The composition for forming the polyimide portion comprises a polyimide precursor and a solvent. <3> like <1> or <2> The composition containing the polyimide portion further includes a migration inhibitor. <4> like <1> to <3> The composition for forming a polyimide portion as described in any one of the following, wherein The glass transfer temperature containing the polyimide portion is below 350°C. <5> like <1> to <4> The composition for forming a polyimide portion as described in any one of the following, wherein The glass transfer temperature containing the polyimide portion is at least 30°C lower than the bonding temperature in the bonding step described above. <6> like <1> to <5> The composition for forming a polyimide portion as described in any one of the following, wherein The joining temperature in the above joining steps is below 380°C. <7> like <1> to <6> The composition for forming a polyimide portion as described in any one of the following, wherein The substrate A described above is in the form of a wafer. <8> like <1> to <7> The composition for forming a polyimide portion as described in any one of the following, wherein The substrate B described above is in the form of a wafer. <9> like <1> to <7> The composition for forming a polyimide portion as described in any one of the following, wherein The substrate B described above is in the form of a wafer. <10> like <1> to <9> In any one of the polyimide-containing compositions, during the bonding step, the temperature of the substrate A containing the polyimide portion is preheated to 70°C or higher. <11> like <1> to <10> The polyimide-containing portion forming composition according to any one of the above-described polyimide-containing portion forming steps includes a planarization step of planarizing the surface of the polyimide-containing portion of substrate A between the above-described polyimide-containing portion forming step and the above-described bonding step. <12> like <11> The composition containing the polyimide portion for forming, wherein The planarization step described above is performed by physical grinding. <13> like <11> The composition containing the polyimide portion for forming, wherein The planarization step described above is performed by chemical grinding. <14> like <1> to <13> The polyimide-containing composition described in any one of the above-mentioned bonding steps is bonded in such a manner that the electrode included in the surface of the substrate A having the polyimide-containing portion is in direct contact with the electrode in the surface of the substrate B having the wiring terminal. <15> like <1> to <14> The composition for forming a polyimide portion as described in any one of the above-mentioned claims further includes a second polyimide portion forming step prior to the above-mentioned bonding step, which forms a second polyimide portion on the surface of the substrate B having the above-mentioned wiring terminals. <16> like <1> to <15> The polyimide-containing composition described in any one of the claims further comprises a photosensitive compound. <17> like <1> to <16> The composition for forming a polyimide portion as described in any one of the following, wherein The above-mentioned polyimide-containing portion forming step includes applying a polyimide-containing portion forming composition to the surface of substrate A having the above-mentioned wiring terminals and heating it. <18> like <17> The composition containing the polyimide portion for forming, wherein The heating temperature mentioned above is below 375℃. <19> A method for manufacturing a joint, comprising: The step of preparing a substrate A with wiring terminals on the side; The step of forming a polyimide-containing portion on the surface of the substrate A having the wiring terminals described above; The step of preparing a substrate B having a side with wiring terminals; and The bonding step involves joining the surface of substrate A containing the polyimide portion to the surface of substrate B containing the wiring terminals. The glass transfer temperature containing the polyimide portion is lower than the bonding temperature in the bonding step described above. <20> A joint, which is by means of <19> It is obtained by the manufacturing method described above. <21> A method for manufacturing a device, comprising: <19> The method for manufacturing the aforementioned joint. <22> A device comprising <20> The aforementioned joint. [Invention Effects]

[0008] According to the present invention, there is a polyimide-containing composition for forming a joint that can obtain a joint with a large maximum peel resistance between two substrates when bonding two substrates, a method for manufacturing a joint using the above-mentioned polyimide-containing composition, a joint obtained by the above-mentioned manufacturing method, a method for manufacturing a device including the above-mentioned joint manufacturing method, and a device including the above-mentioned joint. Simple Explanation of the Diagram

[0009] Figure 1 is a schematic cross-sectional view of the structure of a COC semiconductor device. Figure 2 is a schematic cross-sectional view illustrating the steps of bonding a substrate in a method for manufacturing a polymer-containing composition for forming a polymeric portion according to an embodiment of the present invention. Figure 3 is a schematic cross-sectional view illustrating the steps of bonding a substrate in a method for manufacturing a polymer-containing component of the present invention (a continuation of Figure 2). Figure 4 is a schematic cross-sectional view illustrating the steps of bonding a substrate in a method for manufacturing a polymer-containing composition for forming the present invention, according to one embodiment of the invention (a continuation of Figure 3). Figure 5 is a schematic cross-sectional view of an example of a three-dimensional mounted semiconductor device using TSV. Figure 6 is a schematic cross-sectional view showing the details of the substrate used in the embodiment. Implementation

[0010] The present invention will now be described in detail. The following description of the constituent elements of the present invention is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the designations of groups (atomic groups) without specifying whether they are substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl" means not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this instruction manual, the term "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Furthermore, the light used in exposure can typically be exemplified by the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation. In this manual, the range of values ​​represented by "~" refers to the range that includes the values ​​recorded before and after "~" as the lower and upper limits. In this specification, “(meth)acrylate” means either “acrylate” or “methyl acrylate”, “(meth)acrylic” means either “acrylic” or “methacrylic”, and “(meth)acrylyl” means either “acrylyl” or “methacrylyl”. In this manual, the term "step" is used not only for independent steps, but also for steps that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved. In this instruction manual, solid content refers to the mass percentage of all components other than solvent relative to the total mass of the composition. Furthermore, unless otherwise specified, solid content concentration refers to the concentration at 25°C. Unless otherwise specified, the temperature in this invention is set to 25°C. In this instruction manual, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalents based on gel osmosis chromatography (GPC). In this instruction manual, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 (manufactured by TOSOH CORPORATION) and any of the following protective columns: HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, the precipitate is assumed to be measured using THF (tetrahydrofuran). Furthermore, unless otherwise specified, a UV (ultraviolet) wavelength 254nm detector is used for testing.

[0011] (Contains a polyimide portion forming component) The present invention relates to a method for manufacturing an assembly containing a polyimide portion, which is used in conjunction with the method of manufacturing the assembly, the method comprising: The step of preparing a substrate A having a side with wiring terminals; The step of forming a polyimide-containing portion on the surface of the substrate A having the wiring terminals described above; The steps for preparing a substrate B having a side with wiring terminals; and The bonding step involves joining the surface of substrate A containing the polyimide portion to the surface of substrate B containing the wiring terminals, wherein... The aforementioned polyimide-containing portion is a component formed from the aforementioned polyimide-containing portion forming composition. The glass transfer temperature containing the polyimide portion is lower than the bonding temperature in the bonding step described above.

[0012] By using the polyimide-containing composition of the present invention (hereinafter also simply referred to as "resin composition"), it is possible to manufacture a joint with a large maximum peel resistance between two substrates when bonding two substrates such as wafers to wafers or wafers to a wafer using the polyimide-containing composition. Specifically, by employing a structure in which the glass transition temperature (Tg) of the polyimide portion is lower than the bonding temperature, sufficient fluidity of the polyimide portion during bonding can be ensured, thereby increasing the maximum peel resistance during bonding. In this invention, the bonding temperature refers to the temperature of the polyimide portion during bonding, for example, it can be set to the temperature of the device used during bonding.

[0013] Furthermore, by setting the temperature during bonding to a high temperature, the bonding time can be shortened, and the cycle time of the bonding process can also be reduced. Here, when joining the two substrates as described above, sometimes the alignment accuracy during joining is low, resulting in misalignment of the metal parts such as electrodes on each substrate and exposure of wiring portions. In such cases, the polyimide-containing portions between the wiring portions need to have voltage resistance. Here, for example, if the composition for forming the polyimide portion contains a migration inhibitor, it is believed that the transfer of metal from the metal portion to the polyimide portion can be suppressed, and the voltage withstand performance can be improved. The details of the resin composition of the present invention will be described below.

[0014] <Steps for preparing substrate A> The method for manufacturing a bonding body used in a polyimide-containing composition of the present invention includes the step of preparing a substrate A having a surface with wiring terminals. In the preparation step, substrate A can be manufactured by known methods (e.g., electroplating of a substrate such as a silicon substrate), or it can be obtained by purchasing.

[0015] [Substrate A] The substrate A has a side with wiring terminals. Hereinafter, the wiring terminals in substrate A will also be referred to as wiring terminals A.

[0016] The substrate A can be in the form of a wafer or a chip, but a wafer is also one of the preferred forms of the present invention. In this invention, a wafer refers to a substrate containing semiconductors, including the concept of a panel formed by a plurality of semiconductors and other components. In this invention, a wafer refers to a single piece of semiconductor formed by cutting or the like, which can be a single-sided wafer or a double-sided wafer.

[0017] The shape of substrate A is not particularly limited; for example, it can be a polygonal plate, a disk, or a polyhedron. The thickness of substrate A is preferably 0.1~5mm, and even better if it is 0.2~1mm. In substrate A, terminal A is preferably a columnar electrode. Furthermore, it is preferable that the aforementioned wiring terminal A contains a metal, more preferably at least one metal selected from the group consisting of tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), palladium (Pd), platinum (Pt), cobalt (Co), nickel (Ni), zinc (Zn), ruthenium (Ru), iridium (Ir), rhodium (Rh), lead (Pb), bismuth (Bi), and indium (In), and even more preferably at least one metal selected from the group consisting of copper, tin, and nickel. In this specification, the inclusion of metal X or at least one alloy containing such metal is collectively referred to and simply described as "containing metal X". Additionally, the alloy may contain elements other than those exemplified above. For example, a copper alloy may contain silicon atoms to form a Carson alloy. Furthermore, unavoidably dissolved oxygen or organic residues of the raw material compounds present during precipitation may be present. The aforementioned wiring terminal A may be a wiring terminal comprising a plurality of different components. For example, a portion (hereinafter also referred to as "electrode") is formed on the substrate as an electrode made of a metal such as copper, silver, gold or an alloy containing one or more of these metals, and a portion (hereinafter also referred to as "conductor") is formed on the electrode such as copper as a solder made of a metal such as nickel, tin, lead or an alloy containing one or more of these metals, and the electrode and the conductor can exist in series to form a wiring terminal A. Among these, it is preferable that the aforementioned wiring terminal A is formed by comprising at least a component containing copper and a component containing tin. As an example of a substrate A having such a surface containing wiring terminal A, an example of substrate b) used in the embodiments of this application can be given. In substrate b), conductive paths made of tin are formed on electrodes made of copper.

[0018] Furthermore, the materials used in the electrodes are not particularly limited, and examples include tin, gold, silver, copper, aluminum, tungsten, palladium, platinum, cobalt, nickel, zinc, ruthenium, iridium, rhodium, or alloys thereof. Among these, it is preferable that the electrode contains a metal containing copper, a metal containing aluminum, a metal containing tungsten, a metal containing nickel, or a metal containing gold, with a metal containing copper being even more preferable, and copper being a further preference. It is preferable to use a metal that does not melt during the bonding process as the metal used in the electrode. A melting point of 500°C or higher is preferred, 700°C or higher is more preferred, and 800°C or higher is even more preferred. There is no particular upper limit; for example, 3000°C or lower is preferred. The materials used in the conductive path are not particularly limited, and examples include tin, lead, silver, copper, zinc, bismuth, indium, or alloys thereof. In this invention, tin or tin alloys (metals containing tin) solder are preferred. Recently, technology for lead-free solder that does not use lead has also advanced, making this material a preferred choice. The metal used in the conductive path is preferably molten metal during the bonding step. The melting point of the metal used in the conductive path is preferably below 400°C, more preferably below 300°C, and further preferably below 250°C. Regarding the lower limit of the above melting point, as long as it is a solid at room temperature, the lower limit is not particularly limited; for example, 150°C or higher is preferred. Furthermore, it is preferable that the wiring terminals A are formed in multiples on the substrate A.

[0019] The materials used in substrate A are not particularly limited, such as semiconductor substrates made of silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates made of Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, electrode plates of plasma display panels (PDP), etc., and are not particularly restricted. The substrate may have a close-bonding layer or oxide layer formed of hexamethyldisilazane (HMDS) or similar materials on its surface. In this invention, a semiconductor substrate is particularly preferred, and a silicon substrate (silicon wafer) is even more preferred. Substrate A may have an electronic circuit area containing electronic circuitry. Furthermore, the electronic circuitry may include semiconductor components. It is also preferable that the electronic circuitry is electrically connected to the wiring terminal A. When used as a substrate A-type wafer, the diameter (maximum diameter when substrate A is not circular) can be set to 100mm or more. Furthermore, for large substrates, for example, 200mm or more is preferred, and 250mm or more is even better. There is no particular upper limit, but 2,000mm or less is preferred. When substrate A is a chip, it is preferable to set the diameter (the maximum diameter when substrate A is non-circular) to 7mm or more, more preferably 10mm or more, and even more preferably 20mm or more. As an upper limit, for example, 50mm or less is preferable, 40mm or less is more preferably, and 30mm or less is even more preferably.

[0020] <Steps for forming the polyimide portion> The manufacturing method of the bonding body used in the composition for forming a polyimide portion of the present invention includes a polyimide portion forming step on the surface of the wiring terminal (wiring terminal A) having the above-mentioned substrate A. It is preferable that the polyimide portion is formed in a manner that contacts the aforementioned wiring terminal A, and it is even more preferable that it is formed in a manner that fills the recess between wiring terminals A and wiring terminals A. Furthermore, the polyimide portion only needs to be formed on at least a portion of the aforementioned wiring terminals A. For example, the form formed on all of the aforementioned wiring terminals A is also one of the preferred forms of the present invention. The above-described polyimide-containing portion forming step preferably includes applying a polyimide-containing portion forming composition to the surface of substrate A having the aforementioned wiring terminals and then heating it. Details regarding the application and heating are described below.

[0021] [Contains polyimide portion] The aforementioned component containing the polyimide portion is formed from the aforementioned composition for forming the polyimide portion, and it is preferred that the component is obtained by heating the aforementioned composition for forming the polyimide portion.

[0022] The polyimide-containing part is a component containing polyimide, and may further contain components other than polyimide. Other than polyimide, other components include those not included in the resin composition described later, such as polyimide and its precursors, as well as components whose properties are modified by heating (decomposition, polymerization, structural changes, etc.).

[0023] The glass transfer temperature containing the polyimide portion only needs to be lower than the bonding temperature in the bonding step, but 350°C or lower is preferred, 320°C or lower is even better, and 300°C or lower is even more preferred. There is no specific lower limit to the glass transition temperature mentioned above, but from the point of view of heat resistance, temperatures above 200°C are preferred. From the viewpoint of increasing the maximum peel resistance, it is preferable that the glass transfer temperature containing the polyimide portion is 30°C or more lower than the bonding temperature in the bonding step, more preferably 50°C or more lower, and even more preferably 70°C or more lower. Furthermore, it is preferable that the glass transfer temperature containing the polyimide portion is 30°C or more higher than the bonding temperature in the bonding step.

[0024] The thickness of the polyimide portion is not particularly limited. From the viewpoint of maximizing its physical properties, it is preferable that the thickness immediately before the bonding step (or, in the case of the planarization step described later, the thickness immediately before the planarization step) is 100 nm or more, more preferably 300 nm or more, further preferably 500 nm or more, even more preferably 1 μm or more, and even more preferably 2 μm or more. There is no particular upper limit, but 1 mm or less is preferred, 500 μm or less is more preferably, and 200 μm or less is even more preferably. The film thickness can be measured using a known film thickness measuring device.

[0025] The thermal diffusivity of the polyimide portion in the conjugate, as described later, is preferably 2.0 × 10⁻⁷ m²s⁻¹ or higher, more preferably 3.0 × 10⁻⁷ m²s⁻¹ or higher, and even more preferably 5.0 × 10⁻⁷ m²s⁻¹ or higher. The thermal diffusivity of the polyimide portion can be adjusted, for example, by designing the type of filler material, the particle size of the filler (or the combination of particle sizes when two or more fillers are included), the thermal diffusivity of the filler, the filler content, the structure of the polyimide, the thermal diffusivity of the polyimide, and the polyimide content.

[0026] The polyimide component is preferred as an insulating component. The insulation (resistance) of the polyimide component is not particularly limited, but a volume resistivity of 1×10¹⁵ Ω·cm or higher is preferred, and 1×10¹⁶ Ω·cm or higher is even better. There is no upper limit; practically, it is 1×10¹⁹ Ω·cm or lower. The insulation breaking voltage is preferably 1 kV / mm or higher, and 10 kV / mm or higher is even better. There is no particular upper limit; practically, it is 1000 kV / mm or lower. In this specification, the measurements of volume resistivity and insulation breaking voltage are performed according to JIS C2151:2006 and JIS C2318:2007.

[0027] [Applicable Steps] The polyimide-containing portion forming step preferably includes the step of applying the polyimide-containing portion forming composition (resin composition) of the present invention to the surface of the substrate A having the wiring terminal A (applied step).

[0028] Methods for applying resin compositions to substrate A include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spraying, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spraying, or inkjet coating are preferred. From both the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferable. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spraying, and inkjet coating are preferable; for rectangular substrates, slot coating, spraying, or inkjet coating are preferable. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes. Furthermore, it can also be applied to the method of transferring a coating formed by applying it to a pseudo-support in advance using the above-mentioned method onto a substrate. Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferred in this invention. Furthermore, a step can be performed to remove excess film from the ends of the substrate. Examples of such steps include edge bead rinsing (EBR) and back rinsing. Alternatively, the following pre-wetting step can be adopted: before coating the resin composition onto the substrate, apply various solvents to the substrate to improve the wettability of the substrate, and then coat the resin composition.

[0029] Furthermore, if the resin composition contains a solvent, it may include a step of drying the component (hereinafter also referred to as the "film") made of the resin composition after applying the resin composition to the substrate A. The drying temperature during the drying process is preferably 50~150℃, more preferably 70℃~130℃, and even more preferably 90℃~110℃. Furthermore, drying can be carried out by reducing pressure. As for the drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 2 minutes to 7 minutes are even better.

[0030] The thickness immediately after application (the thickness after drying if the drying step has been performed) is not particularly limited. It can be adjusted appropriately so that the thickness of the polyimide portion obtained becomes the thickness described later.

[0031] The polyimide-containing portion forming step may include a step of patterning a component made of a resin composition. When a photosensitive compound, including a photopolymerization initiator described later, is used as the resin composition, the pattern can be formed by exposure and development. In the polyimide-containing portion formation step, its surface can be planarized after formation. Details of planarization are described later. Furthermore, in the case of patterning, the thickness of the portion removed by development, etc., is not used in the calculation of the film thickness difference (T1-T2) described later.

[0032] [Exposure Steps] The above-mentioned film can be used for an exposure step that selectively exposes the film. That is, the manufacturing method of the polyimide-containing portion (hereinafter also referred to as "cured material") of the composition for forming the polyimide portion of the present invention may include an exposure step of selectively exposing the film formed by the applicable steps. Selective exposure refers to exposing only a portion of the film. Furthermore, through selective exposure, exposed areas (exposed areas) and unexposed areas (non-exposed areas) are formed on the film. The amount of exposure is not particularly specified as long as it is sufficient to harden the resin composition of the present invention. For example, when converted to the exposure energy at a wavelength of 365 nm, 50 to 10,000 mJ / cm² is preferred, and 200 to 8,000 mJ / cm² is even more preferred.

[0033] The exposure wavelength can be appropriately set within the range of 190~1,000nm, with 240~550nm being the optimal range.

[0034] If we describe the exposure wavelength in relation to the light source, examples include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (gamma, h, and i-ray wavelengths), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. For the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is even more preferred. This allows for a particularly high level of exposure sensitivity. Furthermore, the exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed. Examples include exposure using a photomask and exposure based on laser direct imaging.

[0035] <Heating after exposure> The above-mentioned film can be used in the post-exposure heating step (post-exposure heating step). That is, the method for manufacturing a hardened product containing a polyimide portion forming composition of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50℃~140℃, and even better is 60℃~120℃. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and even better if it is 1 minute to 10 minutes. From the initial heating temperature to the maximum heating temperature, the heating rate during the post-exposure heating step is preferably 1~12℃ / min, more preferably 2~10℃ / min, and even more preferably 3~10℃ / min. Furthermore, the heating rate can be appropriately adjusted during the heating process. The heating mechanism used in the post-exposure heating step is not particularly limited, and well-known heating plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to conduct the heating process in a low-oxygen atmosphere by releasing inert gases such as nitrogen, helium, and argon.

[0036] <Developing Steps> The exposed film can be used for the developing step of developing a pattern using a developing solution. That is, the method for manufacturing a hardened material containing a polyimide portion forming component of the present invention may include a developing step of developing a film exposed by an exposure step using a developing solution to form a pattern. By developing, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern. Here, the development that removes the non-exposed portions of the film through the development step is called negative development, and the development that removes the exposed portions of the film through the development step is called positive development.

[0037] [Developing solution] Examples of developing solutions used in the developing step include alkaline aqueous solutions or developing solutions containing organic solvents.

[0038] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. TMAH is more preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0039] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., 3-alkoxy...). Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-alkoxy ... Ethyl ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and, as ethers, preferably, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celecoxyl acetate, ethyl celecoxyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, Examples of preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; as cyclic hydrocarbons, examples include aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene; as sulfides, examples include dimethyl sulfide; as alcohols, examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, and triethylene glycol; and as amides, examples include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0040] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, it is particularly preferred that the developer contains at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developer contains at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and the developer containing cyclopentanone is the most preferred.

[0041] When the developer contains organic solvents, the content of organic solvents relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[0042] The developer may further contain other ingredients. Other components include, for example, well-known surfactants or well-known defoamers.

[0043] [Method for supplying developer] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include immersing the substrate with the film formed in the developer, swirling immersion development using a nozzle to supply the developer to the film formed on the substrate, or continuous supply of developer. There are no particular restrictions on the type of nozzle, such as straight nozzles, spray nozzles, and mist nozzles. From the perspectives of developer penetration, non-image area removal, and manufacturing efficiency, a method of supplying developer using a straight nozzle or a continuous supply method using a spray nozzle is preferable. From the perspective of developer penetration into the image area, a method of supplying developer using a spray nozzle is even better. Alternatively, the developer can be continuously supplied with a straight nozzle, then the substrate can be rotated to remove the developer from the substrate. After rotary drying, the developer can be continuously supplied with a straight nozzle again, and the substrate can be rotated to remove the developer from the substrate. This process can be repeated multiple times. Furthermore, as a method for supplying the developer in the developing step, methods such as continuously supplying the developer to the substrate, maintaining the developer on the substrate in a substantially static state, vibrating the developer on the substrate using ultrasound or the like, and combining these methods are possible.

[0044] The optimal development time is 10 seconds to 10 minutes, with 20 seconds to 5 minutes being even better. There is no specific temperature requirement for the developing solution; it can be performed at an optimal temperature of 10 to 45°C, and even better at 18 to 30°C.

[0045] In the developing step, after treatment with the developer, the pattern can be further cleaned (rinsed) based on the rinsing solution. Alternatively, the rinsing solution can be supplied while the developer that has come into contact with the pattern is not completely dry.

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

[0047] Regarding the organic solvent in the rinsing solution, preferred examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3- Methyl alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl acetone, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and, as ethers, preferably include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celecoxib acetate, ethyl celecoxib acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., etc. And, as ketones, examples preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; as cyclic hydrocarbons, examples preferably include toluene, xylene, anisole, limonene, etc.; as sulfides, dimethyl sulfide, etc., is preferred; as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, triethylene glycol, etc., is preferred; and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferred.

[0048] When the rinsing solution contains an organic solvent, one or more organic solvents may be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are further preferred.

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

[0050] The rinsing solution may further contain other ingredients. Other components include, for example, well-known surfactants or well-known defoamers.

[0051] [Method for supplying flushing fluid] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. Methods include immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by holding the liquid, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle. From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, there are various methods for supplying the rinsing fluid, including spray nozzles, straight nozzles, and mist nozzles. Continuous supply via mist nozzles is preferable, and from the perspective of the rinsing fluid's penetration into the image area, mist nozzles are even better. There are no particular limitations on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles. That is, it is preferable to use a straight nozzle to supply or continuously supply rinsing solution to the exposed film during the rinsing process, and even better to use a spray nozzle to supply rinsing solution. Furthermore, as a method for supplying the rinsing fluid in the rinsing step, methods such as continuously supplying the rinsing fluid to the substrate, maintaining the rinsing fluid in a substantially static state on the substrate, vibrating the rinsing fluid on the substrate using ultrasound or the like, and combining these methods are possible.

[0052] For rinsing time, 10 seconds to 10 minutes is preferred, and 20 seconds to 5 minutes is even better. There is no specific temperature requirement for the rinsing solution, but it can be carried out at a temperature of 10 to 45°C, and more preferably 18 to 30°C.

[0053] <Heating Steps> It is preferable to use the pattern obtained by the developing step (the pattern after rinsing when the rinsing step is performed) for the heating step of heating the pattern (a component made of resin composition) obtained by the above developing step. That is, the method for manufacturing a cured product of a polyimide-containing composition of the present invention may include a heating step of heating a pattern obtained by a developing step. Furthermore, the method for manufacturing a cured product of a polyimide-containing composition of the present invention preferably includes a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by an application step; it is also preferable to include a heating step of heating a film obtained by an application step without a developing step. During the heating step, resins such as polyimide precursors undergo cyclization to become resins such as polyimide. Furthermore, it also involves crosslinking unreacted crosslinking groups in a specific resin or a crosslinking agent other than a specific resin. As for the heating temperature (maximum heating temperature) in the heating step, 375°C or below is preferred, 350°C or below is even better, 300°C or below is even better, and it can also be set to 250°C or below. The lower limit of the above heating temperature is preferably above 160°C, more preferably above 170°C, and even more preferably above 180°C. By adjusting heating conditions such as heating temperature and heating time in the heating process, the glass transition temperature of the polyimide-containing portion can be adjusted. Specifically, it is believed that heating at a higher temperature and for a longer time increases the ring-closure rate of polyimide and raises the glass transition temperature.

[0054] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by heating and the action of an alkali generated by the aforementioned alkali generating agent.

[0055] It is preferable to perform the heating process at a rate of 1 to 12°C / minute, from the initial heating temperature to the maximum heating temperature. A heating rate of 2 to 10°C / minute is more preferred, and 3 to 10°C / minute is even more preferred. Setting the heating rate to 1°C / minute or higher ensures productivity while preventing excessive evaporation of acid or solvent, while setting the heating rate to 12°C / minute or lower reduces residual stress in the hardened material. Furthermore, in the case of an oven capable of rapid heating, it is preferable to increase the temperature by 1 to 8°C / second from the initial temperature to the maximum heating temperature, 2 to 7°C / second is more preferable, and 3 to 6°C / second is even more preferable.

[0056] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating process begins and reaches the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the dried film (layer) is preferred, for example, from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

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

[0058] In particular, when forming multi-layered laminates, from the viewpoint of interlayer tightness, a heating temperature of 30°C or above is preferred, 80°C or above is even better, 100°C or above is further preferred, and 120°C or above is especially preferred. As an upper limit for the above heating temperature, below 350°C is preferred, below 250°C is even better, and below 240°C is further preferred.

[0059] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / minute, holding at 120°C for 60 minutes; increasing the temperature from 120°C to 180°C at a rate of 2°C / minute, holding at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment while irradiating with ultraviolet light. This pretreatment step can improve the membrane's properties. A short pretreatment time of approximately 10 seconds to 2 hours is sufficient, with 15 seconds to 30 minutes being more preferred. The pretreatment can also be performed in two or more stages; for example, a first stage pretreatment can be performed in the range of 100–150°C, followed by a second stage pretreatment in the range of 150–200°C. Furthermore, cooling can be performed after heating, and a cooling rate of 1~5℃ / minute is preferred in this case.

[0060] From the perspective of preventing the decomposition of certain resins, it is preferable to conduct the heating step in a low-oxygen atmosphere by releasing inactive gases such as nitrogen, helium, and argon under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even better. There are no particular limitations on the heating mechanism used in the heating process; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0061] <Post-development exposure steps> The pattern obtained by the developing step (or the washed pattern when the rinsing step is performed) can replace the heating step described above or, in addition to the heating step described above, be used for a post-developing exposure step to expose the pattern after the developing step. That is, the method for manufacturing a cured product of a polyimide-containing composition of the present invention may include a post-development exposure step of exposing a pattern obtained by a development step. The method for manufacturing a cured product of a polyimide-containing composition of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, it can promote, for example, the cyclization reaction of polyimide precursors by photoalkali generating agents, or the removal of acid-decomposing groups by photoacid generating agents. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for all of the pattern to be exposed. The exposure amount in the post-development exposure step is calculated based on the exposure energy at the wavelength where the photosensitive compound is sensitive, and is preferably 50~20,000 mJ / cm2, and even better 100~15,000 mJ / cm2. The post-development exposure step can be performed using the light source described in the above exposure step, with broadband light being preferable.

[0062] <Steps for preparing substrate B> The method for manufacturing a bonding body used in a polyimide-containing composition of the present invention includes the step of preparing a substrate B having a surface with wiring terminals.

[0063] The substrate B can be in the form of a wafer or a chip. The choice depends on the desired bonding design.

[0064] [Substrate B] Substrate B has wiring terminals. Hereinafter, the wiring terminals in substrate B will also be referred to as wiring terminals B.

[0065] The thickness of substrate B is preferably 0.1~5mm, and even better if it is 0.2~1mm. In the joint obtained by the joining steps described later, at least a portion of the wiring terminal B is electrically joined to the wiring terminal A in the substrate A.

[0066] The material used in substrate B is not particularly limited, and the same material as substrate A can be used as an example. Furthermore, the preferred configuration of wiring terminal B is the same as that of wiring terminal A. Substrate B may have an electronic circuit area containing electronic circuitry. Furthermore, the electronic circuitry may include semiconductor components. It is also preferable that the electronic circuitry is electrically connected to the wiring terminals. When used as a substrate B-series wafer, the diameter (maximum diameter when substrate B is not circular) can be set to 100mm or more. Furthermore, for large substrates, for example, 200mm or more is preferred, and 250mm or more is even better. There is no particular upper limit, but 2,000mm or less is preferred. When substrate B is a chip, it is preferable to set the diameter (the maximum diameter when substrate B is non-circular) to 7mm or more, more preferably 8mm or more, and even more preferably 10mm or more. As an upper limit, for example, 50mm or less is preferable, 30mm or less is more preferably, and 20mm or less is even more preferably.

[0067] <Step 2: Formation of the Polyimide Part> The manufacturing method of the bonding body used in the composition for forming the polyimide portion of the present invention further includes, preferably, a second polyimide portion forming step, which forms a second polyimide portion on the surface of the substrate B having the wiring terminals before the bonding step. The second polyimide-containing portion formation step can be performed, for example, by the same method as the polyimide-containing portion formation step of substrate A described above. Here, in the second polyimide-containing portion forming step, the polyimide-containing portion forming composition of the present invention can be used, or other known polyimide-containing portion forming compositions can be used, but it is preferred to use the polyimide-containing portion forming composition of the present invention. In the second polyimide-containing portion formation step, when the polyimide-containing portion formation composition of the present invention is used, the composition of the polyimide-containing portion formation composition of the present invention used in the second polyimide-containing portion formation step may be the same as or different from the composition of the polyimide-containing portion formation composition used in the polyimide-containing portion formation step of substrate A. The second preferred sample containing the polyimide portion is the same as the preferred sample containing the polyimide portion formed in the substrate A described above. In the bonding step described later, it is believed that the adhesion of the bond is improved by bonding the second polyimide-containing portion to at least a portion of the polyimide-containing portion formed in the substrate A.

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

[0069] [Planarization Steps] The method for manufacturing the bonding body used in the composition for forming the polyimide portion of the present invention preferably includes a planarization step of planarizing the surface of the polyimide portion of the substrate A between the above-mentioned polyimide portion forming step and bonding step. In the bonding step described later, it is preferable that the planarized polyimide-containing portion of substrate A is bonded to the surface of substrate B (or, the surface of the second polyimide-containing portion that can be planarized) in contact.

[0070] It is preferable that the wiring terminal A in the substrate A is exposed from the polyimide-containing portion by the above-mentioned planarization. The aforementioned planarization can be achieved through physical grinding methods such as cutting, mechanical grinding, lapping, plasma treatment, and laser ablation, or through chemical grinding methods such as CMP (Chemical Mechanical Polishing). Furthermore, CMP or similar methods can be performed after cutting, combining these techniques. Specifically, for example, one could use a diamond tool to cut the surface containing the polyimide portion, exposing the new surface containing the polyimide portion and the wiring terminal A. By planarizing the wiring terminal A and the polyimide portion in the substrate A to expose the wiring terminal A, a wiring terminal A header based on the planarization of the wiring terminal A and the polyimide portion can be formed. For example, planarization can be achieved using a surface planer. Examples of surface planers include those with diamond tools mounted on the spindle, and examples include the DFS8910, DFS8960, DAS8920, and DAS8930 (all product names) manufactured by DISCO Corporation.

[0071] -TTV- In the planarization step, it is preferable that the polyimide portion and the wiring terminal A are planarized together. As for the degree of planarization, it is preferable that the total thickness variation (TTV) of the polyimide portion and the wiring terminal A is 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. In this invention, TTV refers to dividing the area from the edge of the polyimide portion inwards by more than 1 mm into 2 mm square partitions (when the area of ​​the polyimide portion is too small to be divided into 2 mm square partitions, all areas from the edge of the polyimide portion inwards by more than 1 mm are defined as one partition), measuring the maximum thickness (T1) between one surface and another surface and the minimum thickness (T2) between one surface and another surface in each partition, and calculating the film thickness difference (T) for each partition. The partitions are sorted in descending order of membrane thickness difference (T1-T2). The partition groups are divided into two groups: the top partition (with the largest membrane thickness difference) and the bottom partition (with the smallest membrane thickness difference) and the bottom partition (with the smallest membrane thickness difference) and the bottom partition (with the smallest membrane thickness difference). The remaining partition groups are the arithmetic mean of the membrane thickness differences (T1-T2) of each partition group. In this specification, the TTV containing the polyimide portion as defined herein is sometimes referred to as "zonal evaluation TTV". By setting the TTV containing the polyimide portion below the aforementioned upper limit value, the film thickness becomes substantially uniform, and the adhesion to the substrate B is improved.

[0072] -Ra- In the polyimide-containing portion of the present invention, the surface roughness, i.e., Ra, of the side opposite to the surface in contact with the surface of substrate A is preferably 10 nm or more and 1.5 μm or less. As an upper limit, 1 μm or less is preferred, 500 nm or less is more preferred, 300 nm or less is further preferred, 200 nm or less is even more preferred, 150 nm or less is even more preferred, and 120 nm or less is even more preferred. By setting the surface roughness of the polyimide portion to a value above the aforementioned lower limit, the anchoring effect is activated, thereby improving adhesion to substrate B. Furthermore, by setting the surface roughness to below the aforementioned upper limit value, it is possible to effectively suppress the occurrence of defects such as pores caused by bonding containing bubbles when bonding with substrate B.

[0073] When a second polyimide-containing portion is formed on substrate B, it is preferable to include a second planarization step, which planarizes the surface of the second polyimide-containing portion, between the second polyimide-containing portion formation step and the bonding step. The second planarization step can be performed using the same method as the planarization step in substrate A described above.

[0074] [Jointing Steps] The manufacturing method of the bonding body used in the polyimide-containing composition of the present invention includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion to the surface of the substrate B having the wiring terminal. When the substrate B has a second polyimide-containing portion, the bonding step is a step of bonding the surface of the substrate A having the polyimide-containing portion to the surface of the substrate B having the second polyimide-containing portion.

[0075] By means of bonding, wiring terminal A in substrate A and wiring terminal B in substrate B are electrically bonded. In the above-described bonding step, bonding is performed by having the electrode contained in the surface of the substrate A containing the polyimide portion and the electrode in the surface of the substrate B containing the wiring terminal in direct contact, which is also one of the preferred embodiments of the present invention. That is, it is preferable that neither wiring terminal A nor wiring terminal B has a conductive path. In this invention, by using a glass transfer temperature of the polyimide portion that is lower than the bonding temperature, the adhesion and electrical connection between substrate A and substrate B can be ensured even without using a conductive path.

[0076] It is preferable to use a method that includes heating to perform the bonding, and even better to use a method that includes both heating and pressurization. The bonding temperature is preferably 100°C or higher, more preferably 150°C or higher, and further preferably 180°C or higher. As an upper limit, 450°C or lower is preferred, 400°C or lower is more preferred, 380°C or lower is further preferred, 350°C or lower is especially preferred, 300°C or lower is even more preferred, 280°C or lower is even more preferred, 260°C or lower is even more preferred, and 250°C or lower is even more preferred. As described above, considering the need to melt the conductive path and enable bonding with the electrode, this temperature is preferably near the melting point of the conductive path. There is no particular limit to the heating time during the bonding process, but 5 seconds or more is preferred, 1 minute or more is even better, and 2 minutes or more is even better. As an upper limit, it is actually less than 30 minutes. There are no particular limitations on the heating environment, but it is preferable to perform the heating under reduced pressure while mechanically pressurizing the polyimide-containing portion. As for the ambient pressure, 1×10⁻⁵ mbar or higher is preferred, 1×10⁻⁴ mbar or higher is more preferred, and 5×10⁻⁴ mbar or higher is even more preferred. As for the upper limit, 0.1 mbar or lower is preferred, 1×10⁻² mbar or lower is more preferred, and 5×10⁻³ mbar or lower is even more preferred. It is preferable to clamp two substrates (substrate A and substrate B) for bonding, and it is also 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 further preferably 10 kN or more. As an upper limit, practically it is 100 kN or less. The apparatus used in the bonding step is not particularly limited, and apparatus used in the reflow of electronic components can be used as well.

[0077] Furthermore, during the bonding process, it is preferable that the substrate A containing the polyimide portion is preheated to a temperature of 70°C or higher. Furthermore, if substrate B includes a second polyimide portion, it is preferable that the temperature of substrate B be preheated to above 70°C. The above-mentioned temperatures are preferably above 70℃, and even better above 90℃. However, there is no specific upper limit to the above-mentioned temperatures; temperatures below 130℃ are preferred. By using the above-mentioned pattern, the cycle time of the engagement process can be reduced. Furthermore, the flowability of the polyimide portion during bonding is sometimes improved, and the maximum peel resistance is also increased.

[0078] [Other steps] Furthermore, the manufacturing method of the bonding body used in the polyimide-containing composition of the present invention does not preclude the insertion of other steps between the steps specified above. Also, as a bonding step, the example of bonding substrate A and substrate B facing each other face-to-face has been described, but it is also possible to arrange and connect a plurality of substrates B in parallel relative to substrate A. Alternatively, a configuration in which substrates A and B of corresponding thicknesses are arranged side-by-side and their sides are bonded together can also be cited.

[0079] <Examples of manufacturing methods for joints> The following is an example of a method for manufacturing a joint, illustrated with figures. Figure 2 is a schematic cross-sectional view illustrating a portion of the steps involved in attaching a substrate using a method for manufacturing a bonding body according to an embodiment of the present invention. First, a substrate A (substrate) 1 (Figure 2(a)) is prepared, in which an electronic circuit region 8 is disposed on a silicon wafer 1x, and electrodes 31 (wiring terminals A) are attached therein. An electronic circuit 81, composed of conductors or semiconductors, is formed inside the electronic circuit region 8 of the substrate A1. The method for forming the electronic circuit is not particularly limited, and it can be formed using a specified method. Furthermore, the structure or components of the electronic circuit are not particularly limited; for example, transistors and wiring structures that conduct electricity to the electrodes can be used.

[0080] A resin composition is applied to the electrode-arranged surface (the surface with the electronic circuit area) P0 of the substrate A1 to form a component (resin composition layer) 4 (Fig. 2(b)). The resin composition layer can be heated and dried in this state (drying step). After drying, the resin composition layer 4 can be patterned by photolithography or ion sputtering.

[0081] Then, in this embodiment, the resin composition layer 4 is heated to promote cyclization and form a hardened polyimide-containing portion 41 (Fig. 2(c)). This forms a polyimide-containing portion-distributed substrate 1y in substrate A1, where the polyimide-containing portion 41 is disposed. As shown in this example, the polyimide-containing portion 41 can shrink compared to the resin composition layer 4 by hardening. Although the shrinkage rate is slightly exaggerated in the figures, it is not particularly limited and can be a smaller shrinkage rate, or it can shrink without hardening. Furthermore, the substrate A shown in the figure, as a wiring terminal A, only has electrode 31, but conductive paths can also be formed on electrode 31. The conductive paths can be initially formed on substrate A, or they can be patterned before curing the polyimide-containing portion and the conductive paths can be formed on the patterned portion by electroplating or the like.

[0082] In the polyimide-containing substrate 1y of this embodiment, the heights h1 and h2 of the electrodes 31 are inconsistent. Furthermore, the surface 4a of the polyimide-containing portion is wavy and not flat. In this embodiment, this height inconsistency of the electrodes 31 is eliminated by planarization, exposing the front end surface, and the surface of the polyimide-containing portion is also planarized. It is believed that the adhesion of the substrate is improved by planarizing it in this way. Furthermore, it is believed that even without forming a conductive path, the connection between wiring terminals is improved.

[0083] Figure 3 shows the planarized polyimide-containing substrate (laminated layer) 1z. On the surface 4b of the polyimide-containing portion, the front end 31a of the electrode 31 is exposed, and the entire surface 4b of the polyimide-containing portion is planarized.

[0084] For the multilayer (a planarized substrate containing a polyimide portion) 1z, a substrate B (Fig. 4(a)) is also prepared. The substrate B2 includes a silicon wafer 2x having a through-hole electrode 2y, a circuit wiring region 8 having circuit wiring 81 disposed therein, and electrodes 32 (wiring terminals B) formed in the circuit wiring region 8. In this embodiment, a second polyimide-containing portion 42 is also formed on the surface of substrate B where the wiring terminal B is located, and its surface 2a is planarized in the same way as the surface of the polyimide-containing portion 41 in substrate A. The formation and planarization of the second polyimide-containing portion 42 can be performed by the same method as the formation and planarization of the polyimide-containing portion 41. Thus, by planarizing the surfaces of the polyimide-containing portion 41 and electrode 31 of substrate A and the second polyimide-containing portion 42 and electrode 32 of substrate B, electrical connectivity is improved even in the absence of conductive paths, as in this embodiment. At this time, the portion of the electrode 31 that is positioned (aligned) into a laminate comes into contact with the electrode 32 disposed on the substrate B2. In this case, if at least one of the polyimide portion 41 and the second polyimide portion 42 contains a migration inhibitor, even if a positional shift occurs at the positioning location, the transfer of metal from the electrode 31 (electrode 32) to the polyimide portion 41 (second polyimide portion 42) can be suppressed, and the voltage withstand performance can be improved. Alternatively, a conductive path can be formed on electrode 32 in wiring terminal B. The conductive path can be initially formed on substrate B, or it can be patterned before curing the second polyimide-containing portion, and the conductive path can be formed on the patterned portion by electroplating or the like.

[0085] Next, in this embodiment, the positioned substrate B2 and the laminate 1z are joined by abutting at the bonding surface P1 via the polyimide-containing portion 41 and the second polyimide-containing portion 42 (Figure 4(b)). This forms a bonding body 100 for bonding two substrates. In the bonding body 100, electrodes 31 and 32 are electrically bonded (bonding step). At the same time, the polyimide-containing portion 41 is softened by the above heating, and the surface 4b of the polyimide-containing portion of the laminate 1z is brought into contact with the surface of the substrate B (the surface of the planarized second polyimide-containing portion 42) 2a to form a bond 100. In this invention, it is believed that since the glass transfer temperature containing the polyimide portion is lower than the bonding temperature in the bonding step, the polyimide portion is sufficiently softened, resulting in excellent adhesion. This enables electrical connection between substrate A and substrate B, and achieves a secure fixation between the two.

[0086] In a preferred embodiment of the present invention, since the polyimide-containing surface 4b and the second polyimide-containing surface 2a of the laminate 1z have high flatness, a dense and accurate contact state with the substrate B2 at the contact surface can be obtained. By achieving a denser and more accurate contact state, porosity that is prone to occur at the contact surface can be effectively suppressed.

[0087] (Method for manufacturing the device) The device of the present invention comprises a bonding body obtained by the manufacturing method of the bonding body using the polyimide-containing composition of the present invention. The semiconductor device manufacturing method of the present invention includes the bonding body manufacturing method of the present invention. The devices of this invention include semiconductor devices, electronic devices, etc., with semiconductor devices or electronic devices being preferred. As for devices, examples include those described in "Illustrated Guide to All the Most Advanced Semiconductor Packaging Technologies" edited by the Semiconductor New Technology Research Association (Kogyo Chosakai Publishing Co., Ltd., pp. 8-19, 110-114, 160-165) and "Illustrated Guide to All Surface Treatment Technologies" edited by the Surface Optics Research Institute of Kanto Gakuin University (Kogyo Chosakai Publishing Co., Ltd., pp. 32-41, 56-59). Specifically, examples include using the polyimide-containing portion as an adhesive film to replace the underfill between wafers, or using the polyimide-containing portion as a die bonding film to fix the wafers. Furthermore, the polyimide-containing composition of the present invention can be used in various fields such as the mounting of LED (Light Emitting Diode) components, the mounting of optical components for flat panel displays, and the mounting of power semiconductor packages. Furthermore, for example, the polyimide-containing composition of the present invention can also be preferably used in the three-dimensional mounting of semiconductor devices having through-silicon vias (TSVs). Figure 5 is a schematic cross-sectional view of a three-dimensional mounting device. In this embodiment, a multilayer 101, on which a plurality of semiconductor elements (semiconductor wafers) 101a-101d are stacked, is disposed on a wiring substrate 120. Each of the semiconductor elements 101a-101d is constructed from a semiconductor wafer such as a silicon substrate. The multilayer 101 has a structure for flip-chip bonding of semiconductor elements 101a (without through electrodes) and semiconductor elements 101b-101d (with through electrodes 102b-102d). Connecting pads on the semiconductor element side with through electrodes are connected by metal bumps 103a, 103b, and 103c, such as solder bumps. A resin layer 110 is formed in the gaps between each semiconductor element 101a-101d. The bonding body manufacturing method of the present invention can be used as a method for manufacturing this multilayer. That is, for example, at least one (preferably all) of the resin layers 110 can be made into polyimide-containing portions formed by the composition for forming polyimide-containing portions of the present invention described above. A surface electrode 120a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stack (substrate / substrate stack) 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 substrate via a metal bump 103e such as a solder bump. A resin layer 110a is formed between the insulating layer 115 and the stack 101. The polyimide-containing portion forming composition of the present invention can also be used when bonding the insulating layer 115 and the laminate 101. That is, for example, the resin layer 110a can be provided as the aforementioned polyimide-containing portion. Furthermore, a resin layer 110b is formed between the insulating layer 115 and the wiring substrate 120. The polyimide-containing portion forming composition of the present invention can also be used when bonding the insulating layer 115 and the wiring substrate 120. That is, for example, the resin layer 110b can be provided as the aforementioned polyimide-containing portion.

[0088] (Detailed information about the resin composition) The following describes in detail the components included in the polyimide-containing composition of the present invention. The polyimide-containing composition of the present invention preferably comprises at least one resin (hereinafter also referred to as "specific resin") selected from the group consisting of polyimide and polyimide precursor, and preferably comprises polyimide precursor and solvent. Furthermore, it is preferable that the polyimide-containing composition of the present invention further includes a photosensitive compound. Examples of photosensitive compounds include photopolymerization initiators and photoacid generators, with photopolymerization initiators being preferred.

[0089] <Specific Resin> The resin composition of the present invention preferably contains at least one resin (a specific resin) selected from the group consisting of polyimide and polyimide precursor, and more preferably contains a polyimide precursor. Furthermore, it is preferable for a particular resin to have polymerizable groups, and even more preferable if it contains free radical polymerizable groups. When a particular resin has a free radical polymerizable group, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later, and it is even more preferable that it includes both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Furthermore, the sensitizer described later can be included as needed. For example, a negative photosensitive film can be formed from such a resin composition of the present invention. Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups. In cases where a particular resin has acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid-generating agent described later. Such resin compositions of the present invention can be used to form, for example, chemically amplified positive or negative photosensitive films.

[0090] [Polyimide precursor] There are no particular provisions regarding the type of polyimide precursor used in this invention, but it is preferable to include repeating units represented by the following formula (2). [Chemical Formula 1] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 independently represent hydrogen atoms or monovalent organic groups.

[0091] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, with oxygen atoms being preferred. In formula (2), R 111 represents a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Groups comprising straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof are preferred. Groups comprising aromatic groups with 6 to 20 carbon atoms are even more preferred. The hydrocarbon group in the chain of the above-mentioned straight-chain or branched aliphatic group can be replaced by a group containing heteroatoms, and the hydrocarbon group in the ring members of the above-mentioned cyclic aliphatic group and aromatic group can be replaced by a group containing heteroatoms. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, with the group represented by -Ar-L-Ar- being particularly preferred. Wherein, Ar is independently an aromatic group, L is a single bond, or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of two or more of the above. The preferred ranges are as described above.

[0092] R 111 is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more may be used. Specifically, diamines comprising a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof are preferred, and diamines comprising an aromatic group having 6 to 20 carbon atoms are even more preferred. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing a heteroatom, and the hydrocarbon group in the ring members of the aforementioned cyclic aliphatic and aromatic groups can be replaced by a group containing a heteroatom. Examples of groups containing aromatic groups include the following.

[0093] [Chemical Formula 2] In the formula, A represents a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO 2-, -NHCO-, or combinations thereof. It is even more preferred that the single bond or the group selected from alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO 2-, and -CH 2-, -O-, -S-, -SO 2-, -C(CF 3) 2-, or -C(CH 3) 2- are further preferred. In the formula, * indicates the bonding location with other structures.

[0094] As a diamine, specifically, examples include those selected from 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 isoflurone diamine; m-phenylenediamine 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 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)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane Hexafluoropropane, bis(3-amino-4-hydroxyphenyl) guanidine, bis(4-amino-3-hydroxyphenyl) guanidine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] guanidine, bis[4-(3-aminophenoxy)phenyl] guanidine, bis[4-(2-aminophenoxy)phenyl] guanidine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl guanidine, 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)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- or 2,5-Diaminopropylbenzene, 2,5-Dimethyl-p-phenylenediamine, ethylguanidine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-Diaminobenzene, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diamine Naphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane [3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl At least one diamine selected from the following: 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylbenzene, 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'-hexafluorotriphenyl and 4,4'-diamino-p-tetraphenyl.

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

[0096] Alternatively, the diamine having two or more alkyl diol units in the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may be used more preferably.

[0097] From the viewpoint of the flexibility of the obtained organic membrane, R 111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO 2-, or -NHCO-, or a combination of two or more of the above. Ar-based phenyl groups are preferred, and L-based aliphatic hydrocarbon groups with 1 or 2 carbon atoms that can be substituted with a fluorine atom, or -O-, -CO-, -S-, or -SO 2-, are preferred. Here, aliphatic hydrocarbon groups are preferably alkyl groups.

[0098] Furthermore, from the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by formula (61) is even more preferred. Equation (51) [Chemical Formula 3] In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, at least one of R 50 to R 57 is a fluorine atom, methyl or trifluoromethyl, and * independently represent the bonding sites with nitrogen atoms in formula (2). Examples of monovalent organic groups in R 50 to R 57 include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [Chemical Formula 4] In formula (61), R 58 and R 59 are independently represented by fluorine atoms, methyl or trifluoromethyl atoms, respectively, and * independently represent the bonding sites with nitrogen atoms in formula (2). Examples of diamines providing the structure of formula (51) or (61) include 2,2'-diaminobenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

[0099] In formula (2), R 115 represents a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and the group represented by formula (5) or formula (6) below is even more preferred. In equation (5) or equation (6), * independently represents the bonding location with other structures. [Chemical Formula 5] In formula (5), R112 is a single bond or a divalent linker. It is preferred that the single bond or a 1-10 carbon aliphatic hydrocarbon group that can be replaced by a fluorine atom, -O-, -CO-, -S-, -SO 2- and -NHCO-, and a combination thereof are selected from the base diagram. It is even more preferred that the single bond or a base diagram selected from 1-3 carbon aliphatic alkyl groups that can be replaced by a fluorine atom, -O-, -CO-, -S- and -SO 2- are selected from the group including -CH 2-, -C(CF 3) 2-, -C(CH 3) 2- ...C(CF 3) 2-, -C(CF 3) 2-, -C(C(CF 3) 2-, -C(C(CF 3) 2-, -C(C(CF 3) 2-, -C(C(CF 3) 2-, -C(C(

[0100] Specifically, R 115 can be exemplified by the tetracarboxylic acid residue remaining after the anhydride group is removed from a tetracarboxylic dianhydride. A polyimide precursor containing a structure equivalent to R 115 may contain only one type of tetracarboxylic acid dianhydride residue, or it may contain two or more. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 6] In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.

[0101] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Dihydrides, 2,2-bis(2,3-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 the like having 1 to 6 carbon atoms.

[0102] As a better example, one could also cite tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0103] In formula (2), at least one of R111 and R115 can also have an OH group. More specifically, as R111, residues of diaminophenol derivatives can be cited.

[0104] In formula (2), R113 and R114 each independently represent a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R113 and R114 contains a polymerizable group, and even more preferable that both contain polymerizable groups. It is also preferable that at least one of R113 and R114 contains two or more polymerizable groups. As a polymerizable group, it is a group capable of undergoing a cross-linking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxobutyl, benzo[a]azolyl, block isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a base group having vinyl unsaturated bonds is preferred. Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with the group represented by formula (III) below being preferred.

[0105] [Chemical Formula 7]

[0106] In formula (III), R 200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred. In equation (III), * indicates the bonding site with other structures. In formula (III), R 201 represents a alkyl group with 2 to 12 carbon atoms, -CH 2CH(OH)CH 2-, cycloalkyl group or polyalkylene group. Examples of preferred R 201 include alkylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH 2CH(OH)CH 2-, polyalkylene, alkylene, propylene, -CH 2CH(OH)CH 2-, cyclohexylene, polyalkylene, and alkylene, propylene, or polyalkylene are preferred, with alkylene, propylene, or polyalkylene being further preferred. In this invention, polyalkylene oxide refers to a group formed by the direct bonding of two or more alkylene oxide groups. The alkylene groups in the plurality of alkylene oxide groups contained in the polyalkylene oxide group may be the same or different. When a polyalkoxy group contains multiple alkoxy groups with different alkyl groups, the arrangement of the alkoxy groups in the polyalkoxy group can be random, block-shaped, or alternating. The number of carbon atoms in the above-mentioned alkyl group (including the number of carbon atoms of the substituent if the alkyl group has substituents) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is especially preferred, and 2 is the best. Furthermore, the aforementioned alkyl groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms. Furthermore, the number of polyalkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups formed by the bonding of a plurality of ethyleneoxy and a plurality of propoxy groups are preferred as polyethyleneoxy groups, with polyethyleneoxy or polypropyleneoxy being more preferred, and polyethyleneoxy being even more preferred. Among the groups formed by the bonding of a plurality of ethyleneoxy and a plurality of propoxy groups, the ethyleneoxy and propoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred state of the number of repetitions of ethyleneoxy groups in these groups is as described above.

[0107] In formula (2), when R113 is a hydrogen atom or R114 is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylene unsaturated bond. An example of such a tertiary amine compound with an ethylene unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0108] In formula (2), at least one of R 113 and R 114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. Acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred. From the point of view of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degrading groups include tributoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tributoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0109] Furthermore, it is preferable for the polyimide precursor to have fluorine atoms in its structure. A fluorine atom content of 10% by mass or more in the polyimide precursor is preferred, and 20% by mass or less is also preferred.

[0110] Furthermore, to improve adhesion to the substrate, polyimide precursors can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0111] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in this invention is preferably a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A), the polyimide precursor can further expand the width of the exposure latitude. Equation (2-A) [Chemical Formula 8] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group, preferably both of which contain polymerizable groups.

[0112] A1, A2, R111, R113 and R114 are independently synonyms of A1, A2, R111, R113 and R114 in equation (2), and the preferred range is also the same. R 112 is synonymous with R 112 in equation (5), and the preferred range is also the same.

[0113] Polyimide precursors may contain one repeating unit represented by formula (2), or two or more repeating units. They may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2), polyimide precursors may also contain other types of repeating units.

[0114] As one embodiment of the polyimide precursor in this invention, an example is provided where the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and greater than 90 mol% is especially preferred. There is no particular upper limit to the total content, except that all repeating units of the terminal polyimide precursor can be the repeating units represented by formula (2).

[0115] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of the polyimide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred. In this specification, the molecular weight dispersion is calculated from the weight average molecular weight / number average molecular weight. Furthermore, when the resin composition includes a plurality of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated when the plurality of polyimide precursors are considered as a single resin are each within the aforementioned ranges.

[0116] [Polyimide] The polyimide used in this invention can be an alkali-soluble polyimide or a polyimide soluble in a developer solution with organic solvents as the main component. In this specification, alkali-soluble polyimide refers to polyimide that dissolves at least 0.1 g in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From a pattern-forming point of view, dissolving at least 0.5 g of polyimide is preferred, and dissolving at least 1.0 g of polyimide is further preferred. There is no particular upper limit to the above-mentioned dissolution amount, but less than 100 g is preferred. Furthermore, from the perspective of the strength and insulation of the obtained organic membrane, polyimide with multiple polyimide structures in the main chain is preferred. In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to any other bonded chain.

[0117] -Fluorine atom- From the perspective of the strength of the obtained organic membrane, polyimide with fluorine atoms is also preferable. It is preferable that the fluorine atom is included, for example, in R 132 or R 131 of the repeating unit represented by formula (4) described later, and even more preferably, it is included as a fluorinated alkyl group in R 132 or R 131 of the repeating unit represented by formula (4) described later. The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% or more, and preferably 20% or less.

[0118] -Silicon Atom- From the perspective of the strength of the obtained organic membrane, polyimide with silicon atoms is also preferable. It is preferable that the silicon atom is included, for example, in R 131 of the repeating unit represented by the formula (4) described later, and even more preferably, it is included in R 131 of the repeating unit represented by the formula (4) described later as an organic modified (poly)siloxane structure described later. Furthermore, the aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structures can also be included in the side chains of polyimide, but it is preferable that they are included in the main chain of polyimide. The amount of silicon atoms relative to the total mass of polyimide is preferably 1% or more, and even more preferably 20% or less.

[0119] -Ethylene unsaturated bond- From the perspective of the strength of the obtained organic membrane, polyimide with vinyl unsaturated bonds is preferred. Polyimide can have ethylene unsaturated bonds at the end of the main chain or in the side chain, but it is better to have ethylene unsaturated bonds in the side chain. The aforementioned ethylene-type unsaturated bonds exhibit better free radical polymerization properties. It is preferable that the ethylene unsaturated bond is contained in R 132 or R 131 of the repeating unit represented by formula (4) described below, and it is even more preferable that it is contained in R 132 or R 131 of the repeating unit represented by formula (4) described below as a group having an ethylene unsaturated bond. In these cases, it is preferable that the ethylene unsaturated bond is contained in R 131 of the repeating unit represented by the formula (4) described below, and it is even more preferable that it is contained in R 131 of the repeating unit represented by the formula (4) described below as a group having an ethylene unsaturated bond. Examples of groups having vinyl unsaturated bonds include vinyl, allyl, vinylphenyl, and other vinyl groups that are directly bonded to the aromatic ring and can be substituted, as well as (meth)acrylyl, (meth)acryloxy, and groups represented by formula (IV) below.

[0120] [Chemical Formula 9]

[0121] In formula (IV), R 20 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

[0122] In formula (IV), R 21 represents an alkyl group having 2 to 12 carbon atoms, -O-CH 2CH(OH)CH 2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyl group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group composed of two or more of these. Furthermore, as the aforementioned alkylene groups having 2 to 12 carbon atoms, any one of linear, branched, cyclic, or combined forms of alkylene groups. As for the above-mentioned alkyl groups having 2 to 12 carbon atoms, alkyl groups having 2 to 8 carbon atoms are preferred, and alkyl groups having 2 to 4 carbon atoms are even more preferred.

[0123] Among these, it is preferred that R21 is a group represented by any one of the following formulas (R1) to (R3), with the group represented by formula (R1) being more preferred. [Chemical Formula 10] In formulas (R1) to (R3), L represents a single bond or an alkyl group having 2 to 12 carbon atoms, a (poly)alkyl 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 other structures; and ● represents a bonding site with the oxygen atom bonded to R21 in formula (IV). In formulas (R1) to (R3), the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly) alkoxy group having 2 to 30 carbon atoms in L is the same as the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly) alkoxy group having 2 to 30 carbon atoms in R21 above. In formula (R1), the oxygen atom of the X system is preferred. In equations (R1) to (R3), * is synonymous with * in equation (IV), and the better state is also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide with hydroxyl groups such as phenolic hydroxyl groups with a compound having isocyanate groups and vinyl unsaturated bonds (e.g., ethyl 2-isocyanate 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 ethylene unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide with hydroxyl groups such as phenolic hydroxyl groups with a compound having glycidyl groups and vinyl unsaturated bonds (e.g., glycidyl methacrylate).

[0124] In formula (IV), * indicates the bonding site with other structures, and the bonding site with the main chain of polyimide is preferred.

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

[0126] - Polymerizable groups other than those with ethylene unsaturated bonds- Polyimide can have polymerizable groups other than those with ethylene unsaturated bonds. Examples of polymerizable groups other than those with vinyl unsaturated bonds include cyclic ether groups such as epoxy and cyclobutyl groups, alkoxymethyl groups such as methoxymethyl, and hydroxymethyl groups. In addition to groups having ethylene unsaturated bonds, polymerizable groups, such as R 131 in the repeating unit represented by formula (4) described below, are preferred. The amount of polymerizable groups other than those with vinyl unsaturated bonds relative to the total mass of polyimide is preferably 0.0001~0.1 mol / g, and more preferably 0.001~0.05 mol / g.

[0127] -Polar conversion group- Polyimide can have polar conversion groups such as acid-degradable groups. The acid-degradable groups in polyimide are the same as those described in R 113 and R 114 in the above formula (2), and the preferred state is also the same. Polar conversion groups include, for example, R131, R132, and the end of polyimide in the repeating unit represented by formula (4) described later.

[0128] -Acid Value- When polyimide is used in alkaline development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or higher, 50 mg KOH / g or higher is even better, and 70 mg KOH / g or higher is even more better. Furthermore, the acid value is preferably below 500 mg KOH / g, even better below 400 mg KOH / g, and further preferably below 200 mg KOH / g. Furthermore, when polyimide is used in development with a developer that is mainly composed of organic solvents (e.g., "solvent development" as described below), the acid value of polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The acid value mentioned above is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, considering both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred among the acid groups contained in polyimide, while those with a pKa of 3 to 8 are even better. pKa is the equilibrium constant Ka, which takes into account the dissociation reaction of oxygen releasing hydrogen ions and is expressed by its negative common logarithm, pKa. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD / ChemSketch (registered trademark). Alternatively, the value described in the "5th Revised Edition of the Chemical Handbook: Basics" edited by the Chemical Society of Japan can be consulted. Furthermore, in the case of polybasic acids such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such an acid group, polyimide preferably contains at least one group selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0129] -Phenolic hydroxyl- From the viewpoint of making the development speed of alkaline developer suitable, polyimide with phenolic hydroxyl groups is preferred. Polyimide can have phenolic hydroxyl groups at the end of the main chain or in the side chain. It is preferred that the phenolic hydroxyl group is included, for example, in R 132 or R 131 of the repeating unit represented by formula (4) described below. The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1~30 mol / g, and even more preferably 1~20 mol / g.

[0130] As for the polyimide used in this invention, there is no particular limitation as long as it is a polymer compound having an imide structure, but it is preferable to include the repeating unit represented by the following formula (4). [Chemical Formula 11] In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group. In the case of having a polymerizable group, the polymerizable group may be located on at least one of R 131 and R 132, as shown in formula (4-1) or formula (4-2) below, or it may be located at the end of the polyimide. Equation (4-1) [Chemical Formula 12] In formula (4-1), R 133 is a polymerizable group, and the other groups are synonymous with formula (4). Equation (4-2) [Chemical Formula 13] At least one of R 134 and R 135 is a polymeric group, and if it is not a polymeric group, it is an organic group. The other groups are synonymous with formula (4).

[0131] As polymerizable groups, examples include groups containing the aforementioned ethylene unsaturated bonds or crosslinking groups other than those containing the aforementioned ethylene unsaturated bonds. R 131 represents a divalent organic group. Examples of divalent organic groups that are the same as R 111 in formula (2) can be shown, and the preferred range is also the same. Furthermore, R 131 can be a diamine residue remaining after the amino group of the diamine has been removed. As a diamine, aliphatic, cyclic aliphatic, or aromatic diamines can be cited. As a specific example, R 111 in formula (2) of polyimide precursors can be cited.

[0132] From the viewpoint of more effectively suppressing warping during calcination, R 131 is preferably a diamine residue with at least two alkyl diol units in the main chain. More preferably, it contains a total of two or more diamine residues of either or both of ethylene glycol chains and propylene glycol chains in one molecule. Further preferably, the diamine is a diamine residue that does not contain an aromatic ring.

[0133] Examples of diamines containing a total of two or more ethylene glycol chains or propylene glycol chains in a single molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (these are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but are not limited to these.

[0134] R 132 represents a tetravalent organic group. Examples of tetravalent organic groups that are the same as R 115 in formula (2) can be shown, and the preferred range is also the same. For example, the four bonds of the tetravalent organic group exemplified as R 115 bond with the four -C (=O)- portions in the above formula (4) to form a condensation ring.

[0135] Furthermore, R 132 can be exemplified by tetracarboxylic acid residues remaining after the anhydride group is removed from tetracarboxylic dianhydrides. As a specific example, R 115 in formula (2) of polyimide precursors can be cited. From the viewpoint of the strength of organic films, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0136] It is also preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131, preferred examples include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and as R 132, more preferred examples include the above (DAA-1) to (DAA-5).

[0137] Furthermore, the presence of fluorine atoms in the structure of polyimide is also preferable. The fluorine atom content in polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

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

[0139] Furthermore, to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochloro compounds, and monoactive ester compounds. Among these, monoamines are preferred, and preferred compounds for monoamines 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, 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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and by reacting a plurality of end-capping agents, a plurality of different end groups can be introduced.

[0140] - Acrylimization rate (ring-closure rate) - From the perspective of the obtained organic membrane strength and insulation, the amide ratio (also known as "ring-closing ratio") of polyimide is better if it is above 70%, better if it is above 80%, and better if it is above 90%. There is no specific upper limit to the aceimination rate mentioned above, as long as it is below 100%. The aceimide ratio mentioned above can be measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the peak intensity P1 near 1377 cm⁻¹, representing the absorption peak originating from the amide structure, was determined. Next, the polyimide was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P2 near 1377 cm⁻¹. Using the obtained peak intensities P1 and P2, the amide content of the polyimide can be calculated according to the following formula. Acrylimization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0141] Polyimide may contain all repeating units represented by formula (4) above, including one type of R 131 or R 132, or it may contain two or more different types of repeating units represented by R 131 or R 132 above. Furthermore, polyimide may contain other types of repeating units besides those represented by formula (4) above. Examples of other types of repeating units include, for instance, the repeating unit represented by formula (2) above.

[0142] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine (partially replaced by a monoamine end-capping agent) at low temperature; by reacting a tetracarboxylic dianhydride (partially replaced by an anhydride, a monochloro compound, or a monoactive ester compound end-capping agent) with a diamine at low temperature; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (partially replaced by a monoamine end-capping agent) in the presence of a condensing agent; using... A polyamide precursor is obtained by methods such as obtaining a diester from a tetracarboxylic acid dianhydride and an alcohol, then acetylchlorinating the remaining dicarboxylic acid and reacting it with a diamine (partially replaced by a monoamine end-capping agent); or by methods that completely acetilimate the precursor using known acetilimation reactions; or by methods that stop the acetilimation reaction midway, introducing a partial acetilimate structure; or by methods that introduce a partial acetilimate structure by mixing a fully acetilimated polymer with the polyamide precursor. Furthermore, other known methods for synthesizing polyamides can also be applied.

[0143] The weight-average molecular weight (Mw) of 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 higher, the folding resistance of the cured film can be improved. For obtaining organic films with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or higher 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 molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and further preferably 2.0 or higher. There is no specific upper limit for the molecular weight dispersion of the polyimide; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is further preferred. Furthermore, when the resin composition contains multiple polyimides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility of at least one polyimide are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersibility calculated when the multiple polyimides are considered as a single resin are each within the aforementioned ranges.

[0144] [Methods for manufacturing polyimide precursors, etc.] Polyimide precursors can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine at low temperature; by reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamide, followed by esterification using a condensing agent or alkylating agent; by obtaining a diester from tetracarboxylic dianhydride and alcohol, followed by reaction in the presence of diamine and a condensing agent; and by obtaining a diester from tetracarboxylic dianhydride and alcohol, followed by acid halogenation of the remaining dicarboxylic acid using a halogenating agent and reaction with diamine. Among the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, followed by acid halogenation of the remaining dicarboxylic acid using a halogenating agent and reaction with diamine is preferred. Examples of 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 alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphatidyl chloride. In methods for manufacturing polyimide precursors, it is preferable to use an organic solvent during the reaction. The organic solvent can be one type or two or more types. As an organic solvent, it can be appropriately specified according to the raw material, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In methods for manufacturing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound can be one type or two or more types. Basic compounds can be appropriately specified depending on the raw materials, examples of which include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undecyl-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0145] -End- Capping Agent- In the manufacture of polyimide precursors, etc., it is preferable to seal the residual carboxylic anhydride, anhydride derivatives, or amine groups at the resin end of the polyimide precursor, etc., to further improve storage stability. When sealing the residual carboxylic anhydride and anhydride derivatives at the resin end, end-capping agents include monools, phenols, thiols, benzenethiophenols, and monoamines. From the viewpoint of reactivity and film stability, monools, phenols, or monoamines are preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tertiary butanol, adamantanol, etc. Preferred compounds among phenols include phenol, methoxyphenol, methylphenol, naphth-1-ol, naphth-2-ol, and hydroxystyrene. Preferred compounds among monoamines 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-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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and by reacting a plurality of end-capping agents, a plurality of different end groups can be introduced. Furthermore, when sealing the amine groups at the end of the resin, compounds with functional groups capable of reacting with amine groups can be used for sealing. Preferred sealing agents for amine groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, phthalic anhydride, benzoic anhydride, and 5-norcamphene-2,3-dicarboxylic anhydride. Furthermore, preferred compounds as carboxylic acid chlorides include acetyl chloride, acrylamide chloride, propionyl chloride, methacrylamide chloride, neopentyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamic acid chloride, 1-adamantanemethyl chloride, heptafluorobutyric acid chloride, stearyl chloride, and benzyl chloride.

[0146] -Solid precipitation- In the manufacture of polyimide precursors, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, causing the solid to precipitate and dry, thereby obtaining the polyimide precursor. To improve the purification degree, the operations of redissolving, redepositing, and drying the polyimide precursor may be repeated. In addition, a step of using an ion exchange resin to remove ionic impurities may be included.

[0147] 〔content〕 The content of a specific resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The resin composition of the present invention may contain only one specific resin, or it may contain two or more resins. When two or more resins are contained, the total amount within the above-mentioned range is preferred.

[0148] Furthermore, it is preferable that the resin composition of the present invention contains at least two resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or may contain two or more specific resins, but it is preferred to contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, it is preferable to contain two or more polyimide precursors with different structures derived from dianhydrides (R 115 shown in formula (2) above).

[0149] <Other Resins> The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins"). Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, amine resins, butyral resins, styrene resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained. For example, by replacing the polymerizable compounds described later or by adding a (meth)acrylic resin with a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻³ moles / g or more) with a weight average molecular weight of 20,000 or less to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured material), etc., can be improved. Furthermore, other resins can also be added to the resin composition as dispersants for fillers. In this case, known dispersants for fillers can be used without particular limitation as other resins.

[0150] When the resin composition of the present invention includes other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less relative to the total solid content of the resin composition, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less. Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to provide an embodiment with a low content of other resins. In the above-mentioned embodiment, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 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 two or more other resins are contained, the total amount is preferably within the above-mentioned range.

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

[0152] [Free radical crosslinking agent] The resin composition of the present invention preferably contains a free radical crosslinking agent. Free radical crosslinking agents are compounds possessing free radical polymerizable groups. Preferably, the free radical polymerizable group contains an ethylene unsaturated bond. Examples of such ethylene unsaturated bond groups include vinyl, allyl, vinylphenyl, (meth)acryl, maleicadiimino, and (meth)acrylamine groups. Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the groups containing vinyl unsaturated bonds, and (meth)acryl is more preferred from the viewpoint of reactivity.

[0153] Free radical crosslinking agents are preferably compounds with one or more vinyl unsaturated bonds, but compounds with two or more vinyl unsaturated bonds are even more preferred. Free radical crosslinking agents may also have three or more vinyl unsaturated bonds. As for the compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are even more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (hardened material), it is also preferable that the resin composition of the present invention contains a compound having two ethylene unsaturated bonds and the above-mentioned compound having three or more ethylene unsaturated bonds.

[0154] The molecular weight of the free radical crosslinking agent is preferably below 2,000, more preferably below 1,500, and further preferably below 900. The lower limit of the molecular weight of the free radical crosslinking agent is preferably above 100.

[0155] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, phthalic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can also be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0156] Furthermore, free radical crosslinking agents are preferably compounds with a boiling point of 100°C or higher at normal pressure. Examples include compounds in which ethylene oxide or propylene oxide is added to polyfunctional alcohols such as polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetra(meth)acrylate, neopentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, dinepentyl tetra(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol, or trimethylolpropane followed by (meth)propene Compounds subject to esterification, such as the urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193; the polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490; multifunctional acrylates or methacrylates as products of the reaction between epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds such as glycidyl (meth)acrylate that have cyclic ether groups and vinyl unsaturated bonds.

[0157] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a cycloalis ring and having two or more groups containing ethylene unsaturated bonds, or cardo resins, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

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

[0159] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Patent Application Publication No. 2015 / 199219 are also more readily available and are incorporated herein by reference.

[0160] Furthermore, compounds described in Japanese Patent Application Publication No. 10-062986 as formulas (1) and (2) along with their specific examples, which involve the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol followed by (meth)acrylate esterification, can also be used as free radical crosslinking agents.

[0161] In addition, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

[0162] As free radical crosslinking agents, dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and the structure in which the (meth)acrylic group of the above is linked via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0163] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methacrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six pentenoxy groups, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyleneoxy groups; urethane oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.); NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300; UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon...). Manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

[0164] As free radical crosslinking agents, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, or urethane acrylate compounds with an ethylene oxide backbone 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 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0165] Free radical crosslinking agents can also be free radical crosslinking agents with acid groups such as carboxyl groups and phosphate groups. It is preferable that the free radical crosslinking agent with acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and even more preferable is a free radical crosslinking agent that generates acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of an aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent that generates acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl tetrol or dinepentyl tetrol. Commercially available examples include, for instance, M-510 and M-520, produced by TOAGOSEI CO., Ltd. as polybasic acid-modified acrylic oligomers.

[0166] The preferred acid value of a free radical crosslinking agent with acid groups is 0.1~300 mg KOH / g, and more preferably 1~100 mg KOH / g. If the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability, and consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid values ​​were measured according to the description in JIS K 0070:1992.

[0167] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dimethacrylate can be used. Acrylates, dimethylol-tricyclodecane diacrylates, dimethylol-tricyclodecane dimethacrylates, ethylene oxide (EO) adduct diacrylates of bisphenol A, propylene oxide (PO) adduct diacrylates of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylates, ethylene oxide (EO) modified diacrylates of isocyanuric acid, isocyanuric acid modified dimethacrylates, and difunctional acrylates having ethyl carbamate bonds, and difunctional methacrylates having ethyl carbamate bonds. Two or more of these can be mixed as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain weight of around 200. In the resin composition of the present invention, from the viewpoint of controlling the warping of the elastic modulus of the accompanying pattern (hardener), a monofunctional free radical crosslinking agent can preferably be used as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl (meth)acrylamide, glycidyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactone, and other N-vinyl compounds, allyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, compounds with a boiling point of over 100°C at normal pressure are preferred in order to suppress volatilization before exposure. In addition, examples of allyl compounds, such as diallyl phthalate and trimellitic acid, can be cited as free radical crosslinking agents with two or more functions.

[0168] When a free radical crosslinking agent is present, it is preferable that the content of the agent relative to the total solids content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is further preferred.

[0169] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used simultaneously, it is preferable that their combined dosage falls within the range mentioned above.

[0170] [Other crosslinking agents] It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In this invention, other crosslinking agents refer to crosslinking agents other than the aforementioned free radical crosslinking agents. It is preferable to have a compound having a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by being photosensitive by the aforementioned photoacid generator or photobase generator. It is even more preferable to have a compound having a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the action of an acid or base. It is preferable that the acid or alkali mentioned above is generated by a photoacid generator or a photoalkali generator during the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred. Other crosslinking agents include, for example, compounds that have a structure in which hydrogen atoms of the aforementioned amino groups are replaced by acetoxymethyl, hydroxymethyl, or alkoxymethyl groups by reacting formaldehyde or formaldehyde and alcohol with melamine, urea, urea, alkyl urea, benzoguanamine, or other compounds containing amino groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used. Crosslinking agents that use melamine as the above-mentioned amine-containing compounds are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkyl urea are called urea-based crosslinking agents; crosslinking agents that use alkyl urea are called alkyl urea-based crosslinking agents; and crosslinking agents that use benzoguanidine are called benzoguanidine-based crosslinking agents. In these embodiments, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and it is even more preferable that it contains at least one compound selected from the group consisting of glycourea-based crosslinking agents and melamine-based crosslinking agents described below.

[0171] As a compound containing at least one of alkoxymethyl and acetoxymethyl in this invention, examples of its structure include compounds in which alkoxymethyl or acetoxymethyl is directly substituted on the nitrogen atom or triatom of an aromatic group or a urea structure described below. The alkoxymethyl or acetomethyl group of the above compounds is preferably composed of 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and preferably 2 carbon atoms. The total number of alkoxymethyl and aceoxymethyl groups in the above compounds is preferably 1 to 10, more preferably 2 to 8, and especially preferably 3 to 6. The molecular weight of the above-mentioned compounds is preferably below 1500, and 180~1200 is even more preferred.

[0172] [Chemical Formula 14]

[0173] R 100 indicates alkyl or acetylated. R101 and R102 each represent a monovalent organic group that can bond with each other to form a ring.

[0174] Compounds in which alkoxymethyl or acetomethyl groups are directly substituted with aromatic groups include, for example, compounds with the following general formula.

[0175] [Chemical Formula 15]

[0176] In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl or acetyl group, and R 103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to generate a base-soluble group (e.g., a group that is released under the action of an acid, or a group represented by -C(R 4) 2COOR 5 (R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is released under the action of an acid.)). R 105 independently represents alkyl or alkenyl groups, a, b and c are each independently 1 to 3, d are 0 to 4, e are 0 to 3, f are 0 to 3, a+d are 5 or less, b+e are 4 or less, and c+f are 4 or less. Regarding groups that decompose and produce alkali-soluble groups by the action of acid, groups that are removed by the action of acid, and R5 in the group represented by -C(R4)2COOR5, examples include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39). In the formula, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can bond together to form a ring. As the aforementioned alkyl group, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 5 carbon atoms are even more preferred. The aforementioned alkyl group can be either straight-chain or branched. As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is even more preferred. The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures such as condensed rings. The aryl group with 6 to 30 carbon atoms is preferred, and phenyl is even more preferred. Aryl groups with 7 to 20 carbon atoms are preferred, and aryl groups with 7 to 16 carbon atoms are even more preferred. The aforementioned aryl groups refer to aryl groups substituted with alkyl groups, and the preferred forms of these alkyl and aryl groups are the same as those of the aforementioned alkyl and aryl groups. The alkenyl groups with 3 to 20 carbon atoms are preferred, and those with 3 to 16 carbon atoms are even more preferred. Furthermore, these bases may have known substituents within the scope of achieving the effects of the present invention.

[0177] R 01 and R 02 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, aralkyl or alkenyl groups, respectively.

[0178] The groups that decompose under the action of acid to produce alkali-soluble groups or that are removed under the action of acid are preferably trialkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are trialkyl ester groups or acetal groups.

[0179] Specifically, compounds having an alkoxymethyl group can be exemplified by the following structures. Compounds having an acetoxymethyl group can be exemplified by replacing the alkoxymethyl group in the following compounds with an acetoxymethyl group. Compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule can be exemplified by, but are not limited to, the following.

[0180] [Chemical Formula 16]

[0181] [Chemical Formula 17]

[0182] Compounds containing at least one of alkoxymethyl and aceoxymethyl can be commercially available or synthesized by known methods. From the perspective of heat resistance, compounds in which alkoxymethyl or acetomethyl groups are directly substituted on the aromatic ring or trihalomethane ring are preferred.

[0183] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0184] Specific examples of urea-based crosslinking agents include: monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monoethoxymethylated glycourea, diethoxymethylated glycourea, triethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc. Urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea; Ethylene urea, including monohydroxymethylated ethoxyurea, dihydroxymethylated ethoxyurea, monomethoxymethylated ethoxyurea, dimethoxymethylated ethoxyurea, monoethoxymethylated ethoxyurea, diethoxymethylated ethoxyurea, monopropoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea, and dibutoxymethylated ethoxyurea, are ethoxyurea-based crosslinking agents. Monohydroxymethylated fenprourea, dihydroxymethylated fenprourea, monomethoxymethylated fenprourea, dimethoxymethylated fenprourea, monoethoxymethylated fenprourea, diethoxymethylated fenprourea, monopropoxymethylated fenprourea, dipropoxymethylated fenprourea, monobutoxymethylated fenprourea, or dibutoxymethylated fenprourea are all fenprourea-based crosslinking agents; 1,3-Di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0185] Specific examples of benzoguanidine-based crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0186] Furthermore, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include terephthalic acid, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0187] Other commercially available crosslinking agents can also be used. Among the preferred commercially available agents are 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), 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, and DMOM. -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0188] Furthermore, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxobutane compounds and benzo[a] compounds as other crosslinking agents.

[0189] -Epoxy compounds (compounds containing epoxy groups)- As an epoxy compound, compounds having two or more epoxy groups per molecule are preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions originating from cross-linking, thus minimizing film shrinkage. Therefore, the presence of an epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition of the present invention.

[0190] The presence of polyethylene oxide in the epoxy compound is preferred. This further reduces the elastic modulus and suppresses warpage. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, with 2 to 15 repeating units being preferred.

[0191] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkyl glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones containing epoxy groups such as polymethyl(glycidyloxypropyl)siloxane, but are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (these are product names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, and Rika... Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel). (Manufactured by Nippon Kayaku Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds can also be used more effectively.

[0192] [Chemical Formula 18]

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

[0194] In the above structures, considering both improving heat resistance and elongation, n series 1~2 and m series 3~7 are preferred.

[0195] -Oxycyclic butane compounds (compounds containing oxycyclic butyl groups)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxybutane, 1,4-bis{[(3-ethyl-3-oxetane-butyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetane-butyl)methyl] ester. Specifically, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. are preferred, and these can be used alone or in mixtures of two or more.

[0196] -Benzoyl compounds (compounds containing a benzoyl group)- Benzo[a] compounds are preferred because they do not undergo degassing during curing due to the cross-linking reaction originating from the ring-opening addition reaction, and further reduce thermal shrinkage and inhibit warping.

[0197] Preferred examples of benzo[a] compounds include Pd-type benzo[a], Fa-type benzo[a] (these are product names, manufactured by SHIKOKU CHEMICALS CORPORATION), benzo[a] adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a] compounds. These can be used alone or in mixtures of two or more.

[0198] Relative to the total solids content of the resin composition of the present invention, the content of other crosslinking agents is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, further preferably 0.5-15% by mass, and particularly preferably 1.0-10% by mass. The other crosslinking agents may be only one type or may contain two or more types. When two or more other crosslinking agents are contained, it is preferable that their total content falls within the above-mentioned range.

[0199] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it is preferred to contain a photopolymerization initiator. Photopolymerization initiators are preferably photoradical polymerization initiators. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are photosensitizing to light in the ultraviolet to visible regions are preferred. Alternatively, it can be an activator that interacts with a photoexcited sensitizer to generate active free radicals.

[0200] The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L·mol⁻¹·cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be measured using known methods. For example, it is preferable to measure it using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0201] As photoradical polymerization initiators, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a trimethylolamine skeleton, compounds with a diazole skeleton, compounds with a trihalomethyl skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxide, hexaaryl biimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron-aromatic complexes, etc. For details regarding these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application 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 Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are also incorporated into this specification.

[0202] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0203] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators as described in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, as these are incorporated herein by reference.

[0204] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

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

[0206] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is incorporated into this specification.

[0207] Examples of phosphine oxide initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

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

[0209] Oxime compounds are particularly well-suited as photoradical polymerization initiators. The use of oxime compounds can further and more effectively improve exposure latitude. Oxime compounds are especially advantageous due to their wide exposure latitude (exposure margin) and their function as photocuring accelerators.

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

[0211] Preferred oxime compounds include, for example, compounds with the following structures, or 3-(benzoxyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propoxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoxyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonoxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one, etc. In the resin composition of the present invention, it is particularly preferred to use oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linker within the molecule.

[0212] [Chemical Formula 19]

[0213] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, the photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co.,Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structures can also be used. [Chemical Formula 20]

[0214] Oxime compounds having a cyclohexane ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, which are incorporated herein by reference.

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

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

[0217] As a photopolymerization initiator, oxime compounds containing nitro groups can also be used. It is preferable that the oxime compound containing nitro groups is a dimer. Specific examples of oxime compounds containing nitro groups include the compounds described in paragraphs 0031-0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008-0012, 0070-0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007-0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is also an example of an oxime compound containing nitro groups.

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

[0219] As a photoradical polymerization initiator, oxime compounds with hydroxyl substituents bonded to the carbazole backbone can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, which is incorporated herein by reference.

[0220] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group Ar OX1 with an electron-withdrawing group introduced into the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic group Ar OX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, with acetyl and nitro being preferred. Acetyl is more preferred due to its ease of forming a film with excellent lightfastness, and benzoyl is further preferred. The benzoyl group may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio or amino are even more preferred, and alkoxy, alkylthio or amino are further preferred.

[0221] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and formula (OX2), with the compound represented by formula (OX2) being more preferred. [Chemical Formula 21] In the formula, R X1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkyl hydrogen sulfide, aryl hydrogen sulfide, alkyl sulfinyl, aryl sulfinyl, alkyl sulfonyl, aryl sulfonyl, acetyl, acetoxy, amino, phosphinoyl gruop, aminomethyl, or aminosulfonyl. RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkyl thio, aryl thio, alkyl sulfinyl, aryl sulfinyl, alkyl sulfonyl, aryl sulfonyl, acetoxy, or amino. RX3 to RX14 represent hydrogen atoms or substituents independently, respectively; Among them, at least one of RX10 to RX14 is an electron-withdrawing group.

[0222] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13, and RX14 are preferably hydrogen atoms.

[0223] As a specific example of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated herein by reference, can be cited.

[0224] Examples of preferred oxime compounds include those with specific substituents as disclosed in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups as disclosed in Japanese Patent Application Publication No. 2009-191061, the contents of which are included in this specification.

[0225] From the perspective of exposure sensitivity, photoradical polymerization initiators are preferably selected from compounds in the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetylsinene compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyl acetic acid diazole compounds, and 3-aryl substituted coumarin compounds.

[0226] A further preferred method is to use a trihalomethane trihalomethane initiator, an α-aminoketone compound, an acetophosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, preferably selected from at least one compound in the group consisting of trihalomethane trihalomethane trihalomethane compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. Using a metallocene compound or an oxime compound is even more preferred.

[0227] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (milchnerone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones with aromatic ring condensation such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoin; and benzyl derivatives such as benzyl dimethyl ketal. Additionally, compounds represented by the following formula (I) can also be used.

[0228] [Chemical Formula 22]

[0229] In formula (I), RI00 refers to 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 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 a phenyl or biphenyl group substituted with at least one of the alkyl groups having 1 to 4 carbon atoms; RI01 refers to the group represented by formula (II) or is the same group as RI00; and RI02 to RI04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0230] [Chemical Formula 23]

[0231] In the formula, R I05~R I07 are the same as R I02~R I04 in the above formula (I).

[0232] Furthermore, the photoradical polymerization initiator can also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which is incorporated in this specification.

[0233] As photoradical polymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using such photoradical polymerization initiators, since one molecule of the photoradical polymerization initiator generates two or more free radicals, good sensitivity can be obtained. Furthermore, in the case of using compounds with asymmetric structures, crystallinity decreases while solubility in solvents and the like is improved, making it difficult to precipitate over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and ( ) described in Japanese Patent Application Publication No. 2013-522445. G) Cmpd1-7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators as described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as described in Japanese Patent Publication No. 6469669, etc., are included in this specification.

[0234] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, their total amount within the above-mentioned range is preferred. In addition, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0235] -Thermal polymerization initiator- It is also preferable that the resin composition of the present invention contains a thermal polymerization initiator. As a thermal polymerization initiator, the choice can be made based on the type of polymerizable compound, but thermal free radical polymerization initiators are preferred. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy to initiate or promote the polymerization reaction of polymerizable compounds. Furthermore, the aforementioned photopolymerization initiators sometimes also have the function of initiating polymerization by heat, and thus can sometimes be added as thermal polymerization initiators.

[0236] Examples of known azo compounds and peroxide compounds can be cited as thermal polymerization initiators. Among azo compounds, diazo compounds can be cited. Azo compounds can be compounds containing a cyano group or compounds without a cyano group. Examples of peroxide compounds include ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, diacetyl peroxide, dicarbonate peroxide, and ester peroxide. Commercially available products can also be used as thermal polymerization initiators, such as V-40, V-601, and VF-096 manufactured by FUJIFILM Wako Pure Chemical Corporation, and PERHEXIL O, PERHEXIL D, PERHEXIL I, PERHEXA 25O, PERHEXA 25Z, PERCUMYL D, PERCUMYL D-40, PERCUMYL D-40MB, PERCUMYL H, PERCUMYL P, and PERCUMYL ND. Furthermore, as a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated in this specification, can be cited.

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

[0238] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific photochemical rays and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases. As a usable sensitizer, compounds of the following types can be used: benzophenone, milchnerone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzyllidene, oxonol, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazole methylene azo, phthalocyanine, benzopyran, and indigo. Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminophenylenepropyl (cinnamylidene) Dihydroindone, p-dimethylaminobenzyl dihydroindone, 2-(p-dimethylaminophenylbenzyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated 7-dimethylaminocoumarin Coumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoaniline, N-methylacetamide, 3',4'-dimethylacetamide, etc. Alternatively, other sensitizing pigments can be used. For details regarding the sensitized pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0239] When the resin composition contains a sensitizer, the sensitizer content relative to the total solids content of the resin composition is preferably 0.01~20% by mass, more preferably 0.1~15% by mass, and further preferably 0.5~10% by mass. A single sensitizer may be used, or two or more may be used simultaneously.

[0240] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds containing -SS-, -SO-, -NO-, SH, PH, SiH, and GeH within the molecule, as well as dithiobenzoic acid esters, trithiocarbonates, dithiocarbamates, xanthate compounds, etc., that are used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These agents can generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0241] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated in this specification.

[0242] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids content of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type, or it may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content falls within the above-mentioned range.

[0243] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator is a compound that produces at least one of Brinzyl acid and Lewis acid upon irradiation with light in the range of 200 nm to 900 nm. 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, a photoacid generator capable of generating acid upon photosensitivity is preferred. Examples of acids produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0244] Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, diazonium compounds, and onium salts. From the perspective of sensitivity and storage stability, organohalogen compounds, oxime sulfonates, and onium salts are preferred; from the perspective of the mechanical properties of the formed film, oxime esters are preferred.

[0245] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxyl group, those in which the sulfonic acid of quinone diazide is sulfonated to a monovalent or polyvalent amino group, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonated to a polyhydroxy polyamine group. All functional groups of these polyhydroxy, polyamine, and polyhydroxy polyamine compounds may not be substituted by quinone diazide, but it is preferable that at least 40 moles of the total functional groups are substituted by quinone diazide on average. By containing such a quinone diazide compound, a resin composition sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from a typical ultraviolet mercury lamp can be obtained.

[0246] Specifically, examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, terbutanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, and BisRS. -26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (These are product names, Honshu) The products manufactured by Honshu Chemical Industry Co., Ltd. include, but are not limited to, BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tributylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc.

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

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

[0249] Among these, phenolic compounds and esters with 4-naphthoquinone diazidesulfonyl groups are preferred as quinone diazide compounds. This allows for higher sensitivity and higher resolution to i-ray exposure.

[0250] The content of the quinone diazide compound in the resin composition used in this invention is preferably 1 to 50 parts by weight, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. By setting the content of the quinone diazide compound within this range, the contrast between the exposed and unexposed areas can be obtained, thereby achieving higher sensitivity. In addition, sensitizers or the like can be added as needed.

[0251] Photoacid generators containing oxime sulfonate groups (hereinafter also referred to as "oxime sulfonate compounds") are preferred. There are no particular restrictions on the presence of an oxime sulfonate group in the oxime sulfonate compound, but oxime sulfonate compounds represented by the following formula (OS-1), formula (OS-103), formula (OS-104) or formula (OS-105) are preferred.

[0252] [Chemical Formula 24]

[0253] In formula (OS-1), X3 represents an alkyl, alkoxy, or halogen atom. When multiple X3s are present, they may be identical or different. The alkyl and alkoxy atoms in X3 may have substituents. As the alkyl group in X3, a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in X3, a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in X3, a chlorine or fluorine atom is preferred. In equation (OS-1), m3 represents an integer from 0 to 3, with 0 or 1 being preferred. When m3 is 2 or 3, the complex number of X3 can be the same or different. In formula (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 haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an anthracene group that can 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 haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloaryl group having 6 to 20 carbon atoms.

[0254] In formula (OS-1), compounds of the m3 series 3, X3 series methyl, X3 substitution position is ortho, R34 series straight-chain alkyl with 1 to 10 carbons, 7,7-dimethyl-2-oxonormethylmethyl or p-tolyl are preferred.

[0255] As specific examples of oxime sulfonate compounds represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674 are illustrated in this specification.

[0256] [Chemical Formula 25]

[0257] In formulas (OS-103) to (OS-105), Rs1 represents alkyl, aryl, or heteroaryl; sometimes there are multiple Rs2 that independently represent hydrogen atoms, alkyl, aryl, or halogen atoms; sometimes there are multiple Rs6 that independently represent halogen atoms, alkyl, alkoxy, sulfonic acid, aminosulfonyl, or alkoxysulfonyl; Xs represents O or S; ns represents 1 or 2; and ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbons), aryl group (preferably with 6 to 30 carbons), or heteroaryl group (preferably with 4 to 30 carbons) represented by R s1 may have known substituents within the range that can obtain the effects of the present invention.

[0258] In formulas (OS-103) to (OS-105), Rs2 preferably consists of hydrogen atoms, alkyl groups (preferably with 1 to 12 carbon atoms), or aryl groups (preferably with 6 to 30 carbon atoms), with hydrogen atoms or alkyl groups being more preferred. Sometimes, it is preferred that one or two of the two Rs2 groups in the compound consist of alkyl, aryl, or halogen atoms; more preferably, one alkyl, aryl, or halogen atom; and especially preferably, one alkyl group with the remaining portion consisting of hydrogen atoms. The alkyl or aryl group represented by Rs2 may have known substituents within the range that yields the effects of the present invention. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, with O being preferred. In the above formulas (OS-103) to (OS-105), the ring system containing Xs as a member is a 5-member ring or a 6-member ring.

[0259] In equations (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is 1, which is better. When Xs is S, ns is 2, which is better. In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) represented by R s6 may have substituents. In equations (OS-103) to (OS-105), ms represents an integer from 0 to 6, an integer from 0 to 2 is preferred, 0 or 1 is even better, and 0 is the best.

[0260] Furthermore, the compound represented by the above formula (OS-103) is preferably represented by the compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is preferably represented by the compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is preferably represented by the compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 26]

[0261] In formulas (OS-106) to (OS-111), Rt1 represents alkyl, aryl, or heteroaryl; Rt7 represents a hydrogen atom or a bromine atom; Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl; Rt9 represents a hydrogen atom, a halogen atom, methyl, or methoxy; and Rt2 represents a hydrogen atom or a methyl group. In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, with hydrogen atom being preferred.

[0262] In formulas (OS-106) to (OS-111), R t8 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. It is preferred that the alkyl group has 1 to 8 carbon atoms, a halogen atom, or a phenyl group has 1 to 8 carbon atoms, even more preferred, and a alkyl group has 1 to 6 carbon atoms, with methyl being particularly preferred.

[0263] In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with hydrogen atom being preferred. R t2 represents a hydrogen atom or a methyl group, with hydrogen atom being preferred. Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be either one or a mixture. As specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 are illustrated in this specification.

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

[0265] [Chemical Formula 27]

[0266] In formula (OS-101) or formula (OS-102), Ru9 represents a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acetyl, aminomethyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. It is preferred that Ru9 is cyano or aryl, and it is further preferred that Ru9 is cyano, phenyl, or naphthyl. In formula (OS-101) or formula (OS-102), Ru2a represents alkyl or aryl. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR u5-, -CH 2-, -CR u6H- or CR u6R u7-, and Ru5~R u7 independently represent alkyl or aryl groups.

[0267] In formula (OS-101) or formula (OS-102), Ru1 to Ru4 independently represent hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, amino groups, alkoxycarbonyl groups, alkylcarbonyl groups, arylcarbonyl groups, amide groups, sulfonyl groups, cyano groups, or aryl groups. Two of Ru1 to Ru4 can each bond to form a ring. In this case, the ring can condense to form a condensed ring together with the benzene ring. Preferably, Ru1 to Ru4 are hydrogen atoms, halogen atoms, or alkyl groups; furthermore, it is preferred that at least two of Ru1 to Ru4 are bonded to form an aryl group. It is also preferred that all of Ru1 to Ru4 are hydrogen atoms. All of the above substituents may further have substituents.

[0268] The compound represented by the above formula (OS-101) is more preferably the compound represented by formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure of the oxime or benzothiazole ring (E, Z, etc.) can be either one of them or a mixture thereof. As specific examples of compounds represented by formula (OS-101), compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674 are shown, and such contents are incorporated in this specification. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 28] 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 Kagaku Co., Ltd.).

[0269] Furthermore, as a better example, compounds represented by the following structural formulas can also be cited. [Chemical Formula 29]

[0270] As organohalogenated compounds, examples include Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and MP Hutt's "Jurnal of Heterocyclic". Compounds described in Chemistry 1 (No. 3), (1970), etc., are incorporated herein by reference. In particular, as a preferred example, trihalomethyl-substituted acetazole compounds: S-trimethylamine compounds. More preferably, examples include at least one s-trihalomethane derivative in which a mono-, di-, or trihalomethane-substituted methyl group is bonded to the s-trihalomethane ring. Specifically, examples include 2,4,6-tris(monochloromethyl)-s-trihalomethane, 2,4,6-tris(dichloromethyl)-s-trihalomethane, 2,4,6-tris(trichloromethyl)-s-trihalomethane, 2-methyl-4,6-bis(trichloromethyl)-s-trihalomethane, and 2-n-propyl-4,6-bis(trichloromethyl)-s- Tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl)-2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris(α,α,β-trichloroethyl ... [Phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris-, 2-styryl-4,6-bis(trichloromethyl)-s-tris-, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-tris-, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-, 2-(4-naphthoxy) Naphthyl)-4,6-bis(trichloromethyl)-s-tris, 2-phenylthio-4,6-bis(trichloromethyl)-s-tris, 2-benzylthio-4,6-bis(trichloromethyl)-s-tris, 2,4,6-tris(dibromomethyl)-s-tris, 2,4,6-tris(tribromomethyl)-s-tris, 2-methyl-4,6-bis(tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

[0271] As specific examples of organoborate compounds, Japanese Patent Application Publication Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, 2002-107916, Japanese Patent No. 2764769, and 2002-116539, as well as Kunz, Martin, “Rad Tech’98. Proceeding April”, etc. Organoborates described in publications such as "Chicago" (19-22, 1998), organoboron-strontium complexes or organoboron-oxystrontium complexes described in Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and organoboron-strontium complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553. The contents of this specification include organoboron-phosphorus complexes described in Japanese Patent Application Publication No. 9-188710, organoboron-transition metal coordination complexes described in Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, and Japanese Patent Application Publication No. 7-292014.

[0272] Examples of diazonium compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application Publication No. 2001-132318, as well as diazonium compounds.

[0273] Examples of the aforementioned onium salt compounds include, for instance, the diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al., Polymer, 21, 423 (1980); the ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc.; the phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; the phosphonium salts described in European Patent Nos. 104,143, 339,049, and 410,201; the phosphonium salts described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and the phosphonium salts described in European Patent No. 370,693, etc. The strontium salts described in the specifications of patents No. 390,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, US Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, J. V. V. V. V. V. V. et al., Macromolecules, 10(6), 1307(1977), and J. V. V. V. et al., J. Polymer The selenium salts described in Sci., Polymer Chem. Ed., 17, 1047 (1979), and the arsenic salts, pyridinium salts, and other onium salts described in CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) are included in this specification.

[0274] As onium salts, examples of onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited. [Chemical Formula 30] In formula (RI-I), Ar 11 represents an aryl group having 1 to 6 substituents with 20 or fewer carbon atoms. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 2 to 12 carbon atoms, alkylamino groups with 1 to 12 carbon atoms of alkyl groups or arylamino groups with 6 to 20 carbon atoms of aryl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. Z 11 - represents a monovalent anion, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, thiosulfonic acid ions, and sulfate ions. In terms of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar 21 and Ar 22 each independently represent aryl groups with 1 to 20 carbon atoms that may have 1 to 6 substituents. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkynyl groups with 2 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms of alkyl groups, alkylamino or arylamino groups with 1 to 12 carbon atoms of alkyl groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. Z 21 - represents a monovalent anion, which can be a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, or sulfate ion. From the perspective of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, or carboxylic acid ion are preferred. In formula (RI-III), R 31, R 32, and R 33 each independently represent an aryl or alkyl, alkenyl, or alkynyl group with 1 to 6 substituents and 6 to 20 carbon atoms. Preferably, from the perspective of reactivity and stability, an aryl group is preferred. 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, aryloxy 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, alkylamino or arylamino 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.Z 31 - indicates a monovalent anion, including halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, thiosulfonic acid ions, and sulfate ions. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

[0275] Specific examples of better photoacid generators include the following. [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] [Chemical Formula 34]

[0276] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the resin composition, more preferably at 0.5 to 18% by mass, further preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass. A photoacid generator can be used alone or in combination of several. In the case of a combination of several, the total amount of these generators is preferably within the range described above. Furthermore, it is better to use it in combination with a sensitizer in order to impart photosensitivity to the desired light source.

[0277] <Alkali-generating agents> The resin composition of the present invention may include an alkali generating agent. Here, the alkali generating agent is a compound capable of generating alkali through physical or chemical action. Preferred alkali generating agents for the resin composition of the present invention include thermal alkali generating agents and photo-alkali generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali-generating agent. By containing a thermal alkali-generating agent, the cyclization reaction of the precursor can be promoted by heating, thereby resulting in a cured material with good mechanical properties or chemical resistance, such as good performance as an interlayer insulating film for rewiring layers included in semiconductor packages. As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases produced by a base-generating agent include secondary and tertiary amines. There are no particular limitations on the alkali-generating agent used in this invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, and aceoxyimine compounds. Specific compounds that can be cited as nonionic base generating agents include those represented by formulas (B1), (B2), or (B3). [Chemical Formula 35]

[0278] In formulas (B1) and (B2), Rb1, Rb2, and Rb3 are independently organic groups, halogen atoms, or hydrogen atoms that do not possess a tertiary amine structure. Rb1 and Rb2 do not simultaneously constitute hydrogen atoms. Furthermore, Rb1, Rb2, and Rb3 do not all possess a carboxyl group. Additionally, in this specification, a tertiary amine structure refers to a structure where all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms in a hydrocarbon system. Therefore, this is not limited to the case where the bonded carbon atoms constitute a carbonyl group, i.e., when forming an amide group together with the nitrogen atom.

[0279] In formulas (B1) and (B2), regarding Rb1, Rb2, and Rb3, it is preferable that at least one of them contains a cyclic structure, and it is even more preferable that at least two of them contain a cyclic structure. The cyclic structure can be any of a monocyclic ring or a condensed ring, with a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings being preferred. A 5-membered or 6-membered ring is preferred, with a 6-membered ring being more preferred. A cyclohexane ring or a benzene ring is preferred, with a cyclohexane ring being more preferred.

[0280] More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), alkenyl groups (preferably with 2-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), aryl groups (preferably with 6-22 carbon atoms, more preferably with 6-18 carbon atoms, and further preferably with 6-10 carbon atoms), or arylalkyl groups (preferably with 7-25 carbon atoms, more preferably with 7-19 carbon atoms, and further preferably with 7-12 carbon atoms). These groups may have substituents within the scope of the effects of the present invention. Rb1 and Rb2 may be bonded to each other to form a ring. A nitrogen-containing heterocycle with 4-7 members is preferred as the formed ring. Rb 1 and Rb 2 are preferably straight-chain, branched or cyclic alkyl groups with substituents (preferably 1 to 24 carbons, more preferably 2 to 18 carbons, and even more preferably 3 to 12 carbons), preferably cycloalkyl groups with substituents (preferably 3 to 24 carbons, more preferably 3 to 18 carbons, and even more preferably 3 to 12 carbons), and preferably cyclohexyl groups with substituents.

[0281] Examples of Rb 3 include alkyl groups (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), aryl groups (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-10 carbons), alkenyl groups (preferably with 2-24 carbons, more preferably with 2-12 carbons, and further preferably with 2-6 carbons), and arylalkyl groups (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). The arylalyl group (preferably with 8-24 carbons, more preferably with 8-20 carbons, and further preferably with 8-16 carbons), alkoxy group (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), aryloxy group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-12 carbons), or arylalkoxy group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). Cycloalkyl groups (preferably with 3-24 carbons, more preferably with 3-18 carbons, and further preferably with 3-12 carbons), arylalyl groups, and arylalkoxy groups are preferred. Rb3 may further have substituents within the scope of the effects of this invention.

[0282] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below. [Chemical Formula 36]

[0283] In the formula, Rb 11 and Rb 12, as well as Rb 31 and Rb 32, are the same as Rb 1 and Rb 2 in formula (B1), respectively. Rb 13 is an alkyl group (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), an alkenyl group (preferably with 2-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-12 carbons), or an arylalkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). Substituents may be present within the scope of the effects of this invention. Among these, arylalkyl groups are preferred.

[0284] Rb 33 and Rb 34 are each independently composed of hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 8 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 8 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), arylalkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), and hydrogen atoms.

[0285] Rb 35 series alkyl (preferably 1-24 carbons, more preferably 1-12 carbons, and even more preferably 3-8 carbons), alkenyl (preferably 2-12 carbons, more preferably 2-10 carbons, and even more preferably 3-8 carbons), aryl (preferably 6-22 carbons, more preferably 6-18 carbons, and even more preferably 6-12 carbons), arylalkyl (preferably 7-23 carbons, more preferably 7-19 carbons, and even more preferably 7-12 carbons), with aryl being preferred.

[0286] The compound represented by formula (B1-1) is also better than the compound represented by formula (B1-1a). [Chemical Formula 37]

[0287] Rb 11 and Rb 12 are synonyms of Rb 11 and Rb 12 in equation (B1-1). The preferred components are Rb 15 and Rb 16 series hydrogen atoms, alkyl groups (preferably 1-12 carbons, more preferably 1-6 carbons, and even more preferably 1-3 carbons), alkenyl groups (preferably 2-12 carbons, more preferably 2-6 carbons, and even more preferably 2-3 carbons), aryl groups (preferably 6-22 carbons, more preferably 6-18 carbons, and even more preferably 6-10 carbons), arylalkyl groups (preferably 7-23 carbons, more preferably 7-19 carbons, and even more preferably 7-11 carbons), hydrogen atoms, or methyl groups. Rb 17 series alkyl (preferably 1-24 carbons, more preferably 1-12 carbons, and even more preferably 3-8 carbons), alkenyl (preferably 2-12 carbons, more preferably 2-10 carbons, and even more preferably 3-8 carbons), aryl (preferably 6-22 carbons, more preferably 6-18 carbons, and even more preferably 6-12 carbons), arylalkyl (preferably 7-23 carbons, more preferably 7-19 carbons, and even more preferably 7-12 carbons), wherein aryl is preferred.

[0288] [Chemical Formula 38]

[0289] In formula (B3), L represents a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the connecting chain linking adjacent oxygen and carbon atoms, and the number of atoms in the connecting chain path is 3 or more. Furthermore, RN1 and RN2 independently represent monovalent organic groups.

[0290] In this specification, "linking chain" refers to the shortest (minimum number of atoms) path connecting two atoms or groups of atoms that are linked together. For example, in the compound represented by the following formula, L is composed of phenyl-ethyl groups and has ethyl groups as saturated hydrocarbon groups, the linking chain consists of 4 carbon atoms, and the number of atoms in 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 "linking chain length") is 4. [Chemical Formula 39]

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

[0292] Furthermore, it is preferable that the alkali generating agent contains a compound represented by the following formula (N1). [Chemical Formula 40]

[0293] In formula (N1), RN1 and RN2 independently represent monovalent organic groups, RC1 represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0294] L-type divalent linker, preferably a divalent organic group. A linker chain length of 1 or more is preferred, and 2 or more is even better. As an upper limit, 12 or less is preferred, 8 or less is even better, and 5 or less is further preferred. The linker chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0295] In formula (N1), RN1 and RN2 independently represent monovalent organic groups (preferably with 1-24 carbon atoms, more preferably with 2-18, and further preferably with 3-12 carbon atoms), and hydrocarbon groups (preferably with 1-24 carbon atoms, more preferably with 1-12, and further preferably with 1-10 carbon atoms). Specifically, aliphatic hydrocarbon groups (preferably with 1-24 carbon atoms, more preferably with 1-12, and further preferably with 1-10) or aromatic hydrocarbon groups (preferably with 6-22 carbon atoms, more preferably with 6-18, and further preferably with 6-10 carbon atoms) are preferred. Using aliphatic hydrocarbon groups as RN1 and RN2 results in a highly basic base, which is therefore preferred. Furthermore, aliphatic and aromatic hydrocarbon groups can have substituents, and they can have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or in the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0296] Examples of aliphatic hydrocarbon groups constituting RN1 and RN2 include straight-chain or branched chain alkyl groups, cyclic alkyl groups, combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. Straight-chain or branched chain alkyl groups with 1 to 24 carbon atoms are preferred, 2 to 18 are more preferred, and 3 to 12 are further preferred. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl. Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even more preferred. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The combination of chain alkyl and cyclic alkyl groups with 4 to 24 carbon atoms is preferred, 4 to 18 is more preferred, and 4 to 12 is even more preferred. Examples of the combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. Alkyl groups with 2 to 12 carbon atoms in the chain are preferred, 2 to 6 are more preferred, and 2 to 4 are even more preferred. The alkyl groups with oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. From the perspective of increasing the boiling point of the alkali produced by decomposition (described later), alkyl groups of RN1 and RN2 with 5 to 12 carbon atoms are preferred. In formulations where close adhesion with metals (e.g., copper) is important, alkyl groups with cyclic alkyl groups or alkyl groups with 1 to 8 carbon atoms are preferred.

[0297] RN1 and RN2 can be interconnected to form a ring structure. When a ring structure is formed, oxygen atoms, etc., can be present in the chain. Furthermore, the ring structure formed by RN1 and RN2 can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As for the formed ring structure, a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1) is preferred. Examples include pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazole rings, piperidine rings, piperidine rings, and morpholine rings. Pyrroleline rings, pyrrolidine rings, piperidine rings, piperidine rings, and morpholine rings are particularly preferred.

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

[0299] As a protecting group, a protecting group that decomposes under the action of acid or base is preferred, and a protecting group that decomposes under the action of acid can be given as an example.

[0300] Specific examples of protecting groups include chain-like or cyclic alkyl groups, or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tributyl, and cyclohexyl. Specifically, examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, and more specifically, examples include methoxymethyl (MOM) groups and ethoxyethyl (EE) groups. Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxetyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0301] There are no particular restrictions on the linking group constituting the divalent L, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is even more preferred. The hydrocarbon group may have substituents, and may contain atoms other than carbon atoms in the hydrocarbon chain. More specifically, a hydrocarbon linking group having a divalent oxygen atom in the chain is preferred; an aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group with a divalent oxygen atom in the chain and a divalent aromatic hydrocarbon group is even more preferred; an aliphatic hydrocarbon group with a divalent oxygen atom in the chain is further preferred. It is preferable that these groups do not contain oxygen atoms. The number of carbon atoms in the divalent hydrocarbon linking group is preferred to be 1 to 24, more preferably 2 to 12, and further preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon linking group is preferred to be 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon linking group is preferred to be 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. The number of carbon atoms in the group related to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group (e.g., arylalkyl) is preferred to be 7 to 22, more preferably 7 to 18, and further preferably 7 to 10.

[0302] Specifically, as the linking group L, linear or branched chain alkyl groups, cyclic alkyl groups, combinations of linear and cyclic alkyl groups, alkyl groups having oxygen atoms in the chain, linear or branched chain alkenyl groups, cyclic alkenyl groups, aryl groups, and aryl alkyl groups are preferred. Straight-chain or branched alkyl groups with 1 to 12 carbon atoms are preferred, 2 to 6 are even better, and 2 to 4 are further preferred. Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even better. The combination of chain-like and cyclic-like alkyl groups with groups having 4 to 24 carbon atoms is preferred, 4 to 12 is even better, and 4 to 6 is further preferred. Alkyl groups containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. Alkyl groups containing oxygen atoms in the chain with 1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are even more preferred.

[0303] The linear or branched chain-like alkenyl group with 2 to 12 carbon atoms is preferred, 2 to 6 is more preferred, and 2 to 3 is even more preferred. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, 1 to 6 is more preferred, and 1 to 3 is even more preferred. Cyclic alkenyl groups with 3 to 12 carbon atoms are preferred, and 3 to 6 are even better. The number of C=C bonds in the cyclic alkenyl group is preferably 1 to 6, even better 1 to 4, and even more preferably 1 to 2. For aryl groups, carbon numbers of 6-22 are preferred, 6-18 are even better, and 6-10 are further preferred. Arylalkyl groups with 7 to 23 carbon atoms are preferred, 7 to 19 are even better, and 7 to 11 are further preferred. Among them, chain-like alkylene, cyclic alkylene, alkylene having an oxygen atom in the chain, chain-like alkylene, alkylene, and alkylene alkylene are preferred, and 1,2-alkylene ethylene, propylene diene (especially 1,3-propylene diene), cyclohexadiyl (especially 1,2-cyclohexadiyl), vinylene (especially cis vinylene), phenylene (1,2-phenylene), phenylene methylene (especially 1,2-phenylene methylene), and ethoxyethylene (especially 1,2-ethoxy-1,2-ethylene) are even more preferred.

[0304] Examples of alkali-generating agents can be given below, but the present invention should not be construed as being limited thereto.

[0305] [Chemical Formula 41]

[0306] The molecular weight of the nonionic alkali generator is preferably below 800, more preferably below 600, and further preferably below 500. As a lower limit, 100 or above is preferred, 200 or above is more preferred, and 300 or above is further preferred.

[0307] Preferred compounds as ionic base generators include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0308] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 42]

[0309] Specific examples of imine salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 43]

[0310] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of resin in the resin composition of the present invention. The lower limit is preferably 0.3 parts by weight or more, and 0.5 parts by weight or more is further preferred. The upper limit is preferably 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, and may also be 5 parts by weight or less, or 4 parts by weight or less. One or more alkali-generating agents can be used. When using two or more, the total dosage within the above-mentioned range is preferred.

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

[0312] Examples of preferred 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, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-... Ethyl ethoxypropionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0313] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0314] Examples of ketones that are preferred include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydro L-glucanone.

[0315] Examples of cyclic hydrocarbons, such as aromatic hydrocarbons like toluene, xylene, and anisole, and cyclic terpenes like limonene, are good examples.

[0316] As a class of urethanes, dimethyl urethane can be cited as a preferred example.

[0317] Among the preferred acetamides are 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-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-methoxymorpholine, and N-acetylmorpholine.

[0318] Among urea derivatives, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are good examples.

[0319] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0320] From the perspective of improving the properties of the coating surface, it is better to use a mixture of two or more solvents.

[0321] In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celusone 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, L-glucosidone, and dihydrol-glucosidone, or a mixture of two or more solvents, is preferred. The use of dimethyl sulfoxide and γ-butyrolactone, or the use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

[0322] From the viewpoint of coatability, it is preferable that the solvent content is 5-80% by mass of the total solids concentration of the resin composition of the present invention, more preferably 5-75% by mass, further preferably 10-70% by mass, and even more preferably 20-70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method.

[0323] The resin composition of the present invention may contain only one solvent or may contain two or more solvents. When containing two or more solvents, it is preferable that their total amount is within the above-mentioned range.

[0324] <Metal Adhesion Improver> The resin composition of the present invention preferably includes a metal adhesion improver for enhancing adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having sulfonylurea structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

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

[0326] [Chemical Formula 44]

[0327] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane. Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0328] [Aluminum-based adhesives] Examples of aluminum-based adhesives include tri(acetyl ethyl acetate)aluminum, tri(acetyl acetone)aluminum, and aluminum diisopropyl acetyl ethyl acetate.

[0329] Furthermore, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated in this specification.

[0330] Relative to 100 parts by weight of a specific resin, the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one type or may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0331] <Migration Inhibitors> It is preferable that the resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.

[0332] There are no particular limitations on the use of compounds as migration inhibitors, including those with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, succinazole ring, thiazole ring, pyrazole ring, isosuccinazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thiourea compounds and compounds with hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivatives, and acehydrazine derivatives. 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, as well as tetraazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0333] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

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

[0335] The following compounds can be cited as specific examples of migration inhibitors.

[0336] [Chemical Formula 45]

[0337] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention 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.

[0338] Migration inhibitors can be a single type or two or more. When there are two or more migration inhibitors, it is preferable that their combined number falls within the above-mentioned range.

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

[0340] Specific compounds used as polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallnut phenol, 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-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-8-hydroxyquinoline, etc. Nitro-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5 ...2,4,6-(1H,3H,5-dimethylbenzyl)-1,3,5-tris(2,4,6-dimethylbenzyl)-2,4,6-(1H,3H,5-dimethylbenzyl)-1,3,5-tris(2,4,5-dimethylben H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenanthrene, phenanthrene, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, aluminum N-nitroso-N-phenylhydroxylamine, ammonium N-nitroso-N-phenylhydroxylamine, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Patent Publication No. 2015 / 125469 can also be used, and this information is incorporated herein by reference.

[0341] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention 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.

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

[0343] Acid scavenger To reduce performance changes caused by the transition from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Here, an acid scavenger refers to a compound that can capture acid-generating compounds by being present in the system; compounds with low acidity and high pKa are preferred. As an acid scavenger, compounds having an amino group are preferred, with primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides being more preferred; primary amines, secondary amines, tertiary amines, and ammonium salts are further preferred; and secondary amines, tertiary amines, and ammonium salts are even more preferred. As acid scavengers, preferred examples include compounds having imidazole, diazabicyclic, ononium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives having hydroxyl and / or ether bonds; and aniline derivatives having hydroxyl and / or ether bonds. In the case of an ononium structure, the acid scavenger is preferably a salt of a cation selected from ammonium, diazo, monium, strontium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than that produced by the acid generator.

[0344] Examples of acid scavengers with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers with a diazabicyclic structure include 1,4-diazabicyclic[2,2,2]octane, 1,5-diazabicyclic[4,3,0]non-5-ene, and 1,8-diazabicyclic[5,4,0]undecyl-7-ene. Examples of acid scavengers with a onium structure include tetrabutylammonium hydroxide, triaryl strontium hydroxide, benzoylmethyl strontium hydroxide, and strontium hydroxide with a 2-oxoalkyl group. Specifically, examples include triphenyl strontium hydroxide, tri(tri-butylphenyl) strontium hydroxide, bis(tri-butylphenyl) strontium hydroxide, benzoylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tri(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0345] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N... -Methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinylamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, hyoscyamine, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

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

[0347] The preferred ratio of acid generator to acid scavenger is 2.5 to 300 molar ratio. That is, from the viewpoint of sensitivity and resolution, a molar ratio of 2.5 or higher is preferred; from the viewpoint of suppressing the decrease in resolution caused by the coarsening of the relief pattern over time until heat treatment after exposure, a ratio of 300 or lower is preferred. A molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0348] The resin composition of the present invention may contain fillers. It is preferable for the filler to have thermal conductivity. The filler can be electrically insulating, semiconductor, or conductive. The degree of electrical insulation and conductivity can be appropriately selected according to the design or purpose. For example, in the case of electrically insulating fillers, a lower limit for the volume resistivity of the filler is preferably 1.0 × 10¹¹ Ω·cm or higher, more preferably 3.0 × 10¹¹ Ω·cm or higher, and especially preferably 1.0 × 10¹² Ω·cm or higher. However, there is no particular limit to the upper limit of the volume resistivity; for example, 1.0 × 10¹⁸ Ω·cm or lower is preferred. On the other hand, in the case of semiconductors or conductive fillers, there is no particular limitation on the lower limit of the volume resistivity of the filler, which is actually 1.0 × 10⁻⁷ Ω·cm or higher. Furthermore, it is preferable that the upper limit of the volume resistivity is less than 1.0 × 10¹¹ Ω·cm.

[0349] The thermal diffusivity of the filler is preferably 5.0 × 10⁻⁷ m²s⁻¹ or higher, more preferably 1.0 × 10⁻⁶ m²s⁻¹ or higher, further preferably 2.0 × 10⁻⁶ m²s⁻¹ or higher, and especially preferably 3.0 × 10⁻⁶ m²s⁻¹ or higher. However, there is no particular upper limit to the thermal diffusivity of the filler; for example, 1.0 × 10⁻⁴ m²s⁻¹ or lower is preferred.

[0350] The density of the filler is preferably 4.0 g / cm³ or less, and more preferably 3.0 g / cm³ or less. However, there is no particular lower limit to the density of the filler; for example, 1.0 g / cm³ or more is preferred. Furthermore, when the filler is a porous material or hollow particles with voids or pores, the density of the filler in this specification refers to the density of the solid components constituting the filler.

[0351] Preferably, the filler material comprises 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 such composite compounds. Examples of nitrogen compounds include boron nitride, aluminum nitride, and silicon nitride. Examples of oxygen compounds include metal oxides such as alumina, magnesium oxide, zinc oxide, silicon oxide, beryllium oxide, titanium oxide, copper oxide, and cuprous oxide. Examples of silicon and carbon compounds include silicon carbide. Examples of boron compounds include, for example, titanium boride and other metallic borides. Other carbon compounds include, for example, carbon-based materials dominated by σ bonds, such as diamond. Furthermore, examples of the aforementioned composite compounds include mineral ceramics such as magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, saponite, and ferrite. Furthermore, electrically insulating filler materials can be metal hydroxides such as magnesium hydroxide and aluminum hydroxide.

[0352] Among these, from the viewpoint of thermal conductivity, it is preferable that the filler material includes at least one of ceramics composed of nitrogen compounds, ceramics composed of metal oxides, and metal hydroxides. Furthermore, it is preferable that the filler material includes at least one selected from the group consisting of 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 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, and it is further preferable that it includes at least one of boron nitride, aluminum nitride, silicon nitride, and aluminum oxide. In addition, boron nitride can have any structure such as c-BN (cubic structure), w-BN (wurtzite structure), h-BN (hexagonal structure), r-BN (rhombohedral structure), t-BN (random layered structure). The shape of boron nitride can be spherical or flaky, but any of these shapes can be used. Furthermore, it can also better utilize the IX-3 series manufactured by NIPPON SHOKUBAI CO., LTD.

[0353] Examples of conductive filler materials include carbon-based materials with π bonds, such as graphite, carbon black, carbon fibers (PITCH-based, PAN-based), carbon nanotubes (CNTs), and carbon nanofibers (CNFs). Other filler materials include metals such as silver, copper, iron, nickel, aluminum, and titanium, as well as alloys such as stainless steel (SUS). Additionally, conductive metal oxides such as zinc oxide doped with different elements, or conductive ceramics such as ferromagnets, can also be used as filler materials.

[0354] The filler can be composed of electrically insulating materials such as silicon dioxide coated or surface-treated with semiconductor or conductive thermally conductive particles. Because of this, thermal conductivity and electrical insulation can be easily controlled separately, thus making it easy to adjust both properties. For example, methods for forming a silicon dioxide film on the surface include the water glass method and the sol-gel method.

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

[0356] Fillers can be used to perform surface treatments such as silane coupling, titanate coupling, epoxy treatment, urethane treatment, and oxidation treatment. Surface treatment agents used in these treatments include, for example, polyols, alumina, aluminum hydroxide, silicon dioxide (silica), hydrated silicon dioxide, alkanolamines, stearic acid, organosiloxanes, zirconium oxide, hydrogenated dimethyl silicone oil, silane coupling agents, and titanate coupling agents. Among these, silane coupling agents are preferred.

[0357] Regarding the size of the filler, an average particle size of less than 30 μm is preferred, less than 20 μm is even better, and less than 10 μm is even more preferred. Furthermore, it is preferred that the average particle size of the filler is 0.01 μm or more, even better that it is 0.05 μm or more, further preferred that it is 0.1 μm or more, and especially preferred that it is 0.3 μm or more. The "average particle size" of the filler can be determined by observing the filler in the polyimide portion using a scanning electron microscope (SEM) and by observing the unaggregated portion of the filler particles (primary particles). The average particle size can be calculated as the average of the apparent profiles of each particle observed by SEM, relative to the diameter of the smallest containment circle. Specifically, it can be recorded by the method described in the embodiments described later.

[0358] The filler can comprise a particulate mixture containing at least two particle groups with different particle sizes. The "particle size" of a particular particle group is determined using the same method as the "particle size" of the filler. With this configuration, the spacing between the fillers is reduced compared to a filler containing only a single diameter, as larger particles are interspersed with smaller particles, thus increasing the contact points and improving thermal conductivity. For example, when two particle groups with different particle sizes are mixed, two peaks are observed in the particle size distribution of the filler containing these particle groups. Therefore, the number of peaks in the filler's particle size distribution can be used to determine how many particle groups with different particle sizes are contained in the filler, i.e., the particulate mixture.

[0359] When the particle size distribution of the filler contains multiple peaks, a peak-to-particle size ratio (equivalent to the ratio of the particle sizes at the peak apex to each other) of 1.5 to 50 is preferred between at least two peaks. A lower limit of 2 or higher is preferred, and 4 or higher is even better. An upper limit of 40 or lower is preferred, and 20 or lower is even better. If the peak-to-particle size ratio is within the above range, it prevents large-diameter fillers from becoming coarse particles, and small-diameter fillers from easily occupying the space between large-diameter fillers. Furthermore, regarding the peak intensity ratio between at least two peaks, a ratio of 0.2 to 5.0 for the larger peak relative to the smaller peak is preferred. A lower limit of 0.2 or higher is preferred, and 0.5 or higher is even better. An upper limit of 5.0 or lower is preferred, and 3.0 or lower is even better.

[0360] The filler content is preferably 10% by mass or more, and even more preferably 30% by mass or more, relative to the total solids content of the resin composition. There is no particular upper limit to the above content. From the perspective of processability based on the lithography process, 90% by mass or less is preferred, and 75% by mass or less is even better. When a resin composition contains fillers, the description of the content of components other than fillers as "relative to the total solids content of the resin composition" is changed to "the total mass of fillers removed from the total solids content of the resin composition".

[0361] The proportion of particles with a diameter of 0.5 to 15 μm in all fillers is preferably 50% by mass or more, and more preferably 80% by mass or more. This proportion can be set to an upper limit of 100% by mass, or to 99% by mass or less. A proportion of 99% by mass or less is preferred, and 95% by mass or less is further preferred.

[0362] As described above, one or more fillers can be used in combination, and when two or more fillers are included, the total amount of such fillers is preferably within the above range.

[0363] <Other Additives> The resin composition of the present invention can be formulated with various additives as needed within the scope of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the physical properties of the membrane can be adjusted. Regarding these components, for example, reference can be made to paragraph 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, it is preferable that their total amount is 3% by mass or less of the solid content of the resin composition of the present invention.

[0364] [Surfactants] As surfactants, various surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. These surfactants can be nonionic, cationic, or anionic.

[0365] By including a surfactant in the photosensitive resin composition of the present invention, the solution properties (especially flowability) when preparing a coating solution are further improved, thereby further improving the uniformity of the coating thickness or the liquid-saving properties. That is, when a coating solution containing a surfactant is used to form a film, the interfacial tension between the coated surface and the coating solution decreases, improving the wettability of the coated surface and thus enhancing the coatability of the coated surface. Therefore, a film with a smaller thickness variation and greater uniformity can be formed more effectively.

[0366] Examples of fluorinated surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO.,LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorinated surfactants can also use 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, the contents of which are incorporated herein by reference. As a fluorinated surfactant, block polymers can also be used. For example, the compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and such contents are incorporated into this specification. Fluorinated surfactants can also preferably use repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propoxy groups). Examples of the following compounds can also be used as fluorinated surfactants in this invention. [Chemical Formula 46]

[0367] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Regarding fluorinated surfactants, fluorinated polymers with vinyl unsaturated groups in their side chains can also be used as fluorinated surfactants. Specific examples include 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. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

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

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

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

[0371] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissan Chemical Industries, Ltd.), etc.

[0372] As cationic surfactants, examples include organosiloxane polymers such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No.75, No.77, No.90, and No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0373] As anionic surfactants, examples include WO04, WO05, WO17 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI CO.,LTD.).

[0374] A single surfactant can be used, or a combination of two or more surfactants can be used. The surfactant content is preferably 0.001~2.0% by mass relative to the total solids content of the composition, and even more preferably 0.005~1.0% by mass.

[0375] [Higher fatty acid derivatives] To prevent polymerization hindrance caused by oxygen, the resin composition of the present invention may contain higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide, which are biased towards the surface of the resin composition of the present invention during the drying process after coating.

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

[0377] When the resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above range.

[0378] [Ultraviolet absorber] The composition of this invention may include a UV absorber. As a UV absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other UV absorbers can be used. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0379] Examples of acrylonitrile-based UV absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In addition, examples of triphenyl terpenoid ultraviolet absorbers include mono(hydroxyphenyl)triphenyl compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl. 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triphenyl, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl, etc., are bis(hydroxyphenyl)triphenyl compounds; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triphenyl, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triphenyl, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triphenyl, etc., are tri(hydroxyphenyl)triphenyl compounds, etc.

[0380] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When it does contain an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present invention is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

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

[0382] As usable organotitanium compounds, those with organic groups bonded to titanium atoms via covalent or ionic bonds can be cited. Specific examples of organotitanium compounds are shown in I) to VII) below. I) Titanium chelate compounds: Among these, titanium chelate compounds with two or more alkoxy groups are preferred, considering the good storage stability of the resin composition and the ability to obtain good hardened patterns. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(2,4-glutarate)di(n-butoxy) titanium, bis(2,4-glutarate)diisopropoxy titanium, bis(tetramethylheptyl ester)diisopropoxy titanium, and bis(ethyl acetate)diisopropoxy titanium. II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc. III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: for example, tris(dioctyl phosphate) isopropoxy titanium, tris(dodecylbenzenesulfonate) isopropoxy titanium, etc. V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc. VI) Tetraacetone titanium compounds: such as tetraacetone titanium, etc. VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0383] Among these, from the viewpoint of exhibiting better drug resistance, it is preferable that at least one compound selected from the group consisting of I) titanium chelates, II) tetraalkoxy titanium compounds and III) diacetic titanium compounds, as organotitanium compounds. In particular, bis(ethyl acetate) diisopropoxy titanium, tetra(n-butoxy) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium are preferred.

[0384] When incorporating organotitanium compounds, the amount of these compounds relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 2 parts by weight. When the amount of these compounds is 0.05 parts by weight or more, the resulting hardened pattern exhibits better heat resistance and chemical resistance. On the other hand, when the amount is 10 parts by weight or less, the composition exhibits better storage stability.

[0385] [Antioxidants] The composition of this invention may include an antioxidant. By including an antioxidant as an additive, the elongation characteristics of the hardened film or its adhesion to metallic materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Hindered phenolic compounds are preferred. Compounds having a substituent at the position (ortho) adjacent to the phenolic hydroxyl group are preferred. As the aforementioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenolic group and a phosphite group within the same molecule are also preferred as antioxidants. Additionally, phosphorus-based antioxidants are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphine-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-heptacyclic-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Additionally, the composition of the present invention may contain potential antioxidants as needed. As potential antioxidants, examples include compounds in which the site where the antioxidant functions is protected by a protecting group, and which function as antioxidants by removing the protecting group through heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst. Examples of potential antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219, the contents of which are incorporated herein by reference. Commercially available examples of potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by formula (3).

[0386] [Chemical Formula 47]

[0387] In general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R6 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R7 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), or an organic group containing at least one of oxygen atoms and nitrogen atoms in a 1 to 4 valence. k represents an integer from 1 to 4.

[0388] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic or phenolic hydroxyl groups in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metallic materials.

[0389] Since it can act on both resin and metal materials simultaneously, integers from 2 to 4 in the k-series are preferred. Examples of R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and it may further have substituents. Among these, alkyl ether and -NH- are preferred from the viewpoint of solubility in the developer or metal adhesion, while -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion based on metal misalignment.

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

[0391] [Chemical Formula 48]

[0392] [Chemical Formula 49]

[0393] [Chemical Formula 50]

[0394] [Chemical Formula 51]

[0395] The amount of antioxidant added relative to 100 parts by weight of a specific resin is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, elongation characteristics or improved adhesion to metal materials can be easily obtained even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved through interaction with photosensitizers. Only one type of antioxidant may be used, or two or more types may be used. When using two or more types, the total amount within the above-mentioned range is preferred.

[0396] [Anticoagulant] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0397] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination. The composition of the present invention may or may not contain coagulation inhibitors. When it does contain coagulation inhibitors, the content of coagulation inhibitors relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.

[0398] [Phenolic compounds] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION).

[0399] In this invention, a single phenolic compound may be used alone, or two or more may be used in combination. The composition of the present invention may or may not contain phenolic compounds. When phenolic compounds are included, the content of phenolic compounds relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0400] [Other polymers] Other examples of polymeric compounds include silicone resins, (meth)acrylic acid polymers copolymerized from (meth)acrylic acid, phenolic varnish resins, soluble phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may also be modifiers incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0401] In this invention, other polymer compounds can be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymeric compounds. When other polymeric compounds are included, the content of other polymeric compounds relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0402] <Properties of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by utilizing the concentration of the solid components in the resin composition. From the viewpoint of coating film thickness, 1,000 mm² / s to 12,000 mm² / s is preferred, 2,000 mm² / s to 10,000 mm² / s is more preferred, and 2,500 mm² / s to 8,000 mm² / s is even more preferred. Within the above range, it is easy to obtain a coating film with high uniformity. If it is 1,000 mm² / s or more, it is easy to coat with a film thickness required for use as an insulating film for rewiring, for example, and if it is 12,000 mm² / s or less, a coating film with excellent surface morphology can be obtained.

[0403] <Restrictions on the substances contained in resin components> It is preferable that the moisture content of the resin composition of the present invention is less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining moisture content include adjusting the humidity in storage conditions and reducing the porosity of the storage container.

[0404] From an insulation point of view, it is preferable that the metal content of the resin composition of the present invention is less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained in the form of complexes of organic compounds and metals. When multiple metals are included, it is preferable that the total amount of these metals is within the above-mentioned range.

[0405] Furthermore, as a method for reducing unintentionally included metallic impurities in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and performing distillation in an apparatus with a lining such as polytetrafluoroethylene to suppress contamination as much as possible.

[0406] In the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, it is preferable that the halogen atom content is less than 500 ppm by mass, more preferably less than 300 ppm by mass, and further preferably less than 200 ppm by mass. Of this, it is preferable that the content of halide ions is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromide ions, is within the above-mentioned ranges. Ion exchange treatment is a good example of a method to regulate the content of halogen atoms.

[0407] As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, as a container, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, it is preferable to use a multi-layer bottle with an inner wall made of six layers of six different resins or a bottle with a seven-layer structure made of six different resins. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0408] <Curing of resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The hardened product of the present invention is a hardened product formed by hardening the resin composition of the present invention. The curing of the resin composition is preferably based on heating, with a heating temperature in the range of 120°C to 400°C being more preferred, in the range of 140°C to 380°C being further preferred, and in the range of 170°C to 350°C being particularly preferred. The morphology of the cured resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured composition is preferably in film form. Furthermore, the shape of the cured composition can be selected according to applications such as forming a protective film on a wall surface, forming a via hole for conduction, adjusting impedance or electrostatic capacitance or internal stress, or imparting heat dissipation function through pattern processing of the resin composition. The film thickness of the cured composition (the film composed of the cured composition) is preferably 0.5 μm or more and 150 μm or less. It is preferable that the shrinkage rate of the resin composition of the present invention during curing is 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated by the following formula. Shrinkage rate [%] = 100 - (Volume after hardening ÷ Volume before hardening) × 100

[0409] <Properties of cured resin compositions> The amide reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, it sometimes results in a cured product with excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0410] (Manufacturing method of the joint) The manufacturing method of the bonding body of the present invention includes: a step of preparing a substrate A having a surface having wiring terminals; a step of forming a polyimide-containing portion on the surface of the substrate A having the wiring terminals; a step of preparing a substrate B having a surface having wiring terminals; and a bonding step of bonding the surface of the substrate A having the polyimide-containing portion with the surface of the substrate B having the wiring terminals, wherein the glass transfer temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step. The detailed contents of substrate A, substrate B and each step in the manufacturing method of the bonding body of the present invention are the same as those of substrate A, substrate B and each step in the manufacturing method of the bonding body used in the polyimide-containing composition of the present invention, and the preferred embodiment is also the same.

[0411] (Joint) The bonding system of the present invention is a bonding body obtained by the bonding body manufacturing method of the present invention. The preferred form of the joint is the same as the preferred form of the joint used in the manufacturing method of the joint in the composition for forming polyimide portion of the present invention described above. [Example]

[0412] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0413] <Synthetic Exam...

Claims

1. A composition for forming a polyimide portion, used in a method for manufacturing a bond comprising the following steps: a step of preparing a substrate A having a surface having wiring terminals; a step of forming a polyimide portion on the surface of the substrate A having the wiring terminals; a step of preparing a substrate B having a surface having wiring terminals; and a bonding step of bonding the surface of the substrate A having the polyimide portion with the surface of the substrate B having the wiring terminals, wherein the polyimide portion is a component formed by the composition for forming a polyimide portion, the glass transition temperature of the polyimide portion is lower than the bonding temperature in the bonding step, the composition for forming a polyimide portion comprises a polyimide precursor and a polymerization initiator, and the polyimide precursor has a repeating unit represented by formula (2-A): Formula (2-A) In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group.

2. The polyimide-containing composition as described in claim 1 further comprises a polymeric compound.

3. The polyimide-containing composition as described in claim 1 further comprises a solvent.

4. The polyimide-containing composition as described in claim 1 or claim 3, further comprising a migration inhibitor.

5. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein the glass transfer temperature of the aforementioned polyimide portion is 350°C or below.

6. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein the glass transfer temperature of the polyimide portion is at least 30°C lower than the bonding temperature in the aforementioned bonding step.

7. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein the bonding temperature in the aforementioned bonding step is 380°C or below.

8. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein the aforementioned substrate A is in the form of a wafer.

9. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein the aforementioned substrate B is in the form of a wafer.

10. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein the aforementioned substrate B is in the form of a wafer.

11. The polyimide-containing composition as described in claim 1 or claim 3, wherein, in the bonding step, the temperature of the substrate A having the polyimide-containing portion is preheated to 70°C or higher.

12. The composition for forming a polyimide portion as described in claim 1 or claim 3, wherein between the aforementioned polyimide portion forming step and the aforementioned bonding step, a planarization step is included to planarize the surface of the polyimide portion of substrate A.

13. The polyimide-containing composition as described in claim 12, wherein the aforementioned planarization step is performed by physical grinding.

14. The polyimide-containing composition as described in claim 12, wherein the aforementioned planarization step is performed by chemical polishing.

15. The polyimide-containing composition as described in claim 1 or claim 3, wherein in the aforementioned bonding step, the electrodes included in the surface of the substrate A having the polyimide-containing portion are in direct contact with the electrodes in the surface of the substrate B having the aforementioned wiring terminals.

16. The polyimide-containing composition as described in claim 1 or claim 3, further comprising, prior to the aforementioned bonding step, a second polyimide-containing portion forming step of forming a second polyimide-containing portion on the surface of the aforementioned substrate B having the aforementioned wiring terminals.

17. The polyimide-containing composition as described in claim 1 or claim 3, further comprising a photosensitive compound.

18. The polyimide-containing composition as described in claim 1 or claim 3, wherein the aforementioned polyimide-containing composition forming step includes applying the polyimide-containing composition to the surface of substrate A having the aforementioned wiring terminals and heating it.

19. The polyimide-containing composition as described in claim 18, wherein the heating temperature during the aforementioned heating is 375°C or below.

20. A method for manufacturing a joint, comprising: The step of preparing a substrate A with wiring terminals; The process includes: forming a polyimide-containing portion on the surface of substrate A having the aforementioned wiring terminals; preparing a substrate B having the surface having the wiring terminals; and joining a bonding step of joining the surface of substrate A having the polyimide-containing portion with the surface of substrate B having the aforementioned wiring terminals. The glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step. The polyimide-containing portion is formed by a composition for forming a polyimide-containing portion. The composition for forming a polyimide-containing portion includes a polyimide precursor and a polymerization initiator, and the polyimide precursor has repeating units represented by formula (2-A): Formula (2-A) In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group.

21. A joint obtained by the method of manufacturing the joint described in claim 20.

22. A method of manufacturing a device, comprising the method of manufacturing the assembly described in claim 20.

23. A device comprising the junction described in claim 21.

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