Method for producing bonded body, bonded body, method for producing device, and resin composition

Abstract

Provided is a method for producing a bonded body, the method comprising: a step for preparing a base material A having a surface provided with an electrode A; a step for forming an organic insulation region, wherein the organic insulation region is formed on the surface provided with the electrode A; a step for preparing a base material B having a surface provided with an electrode B; and a bonding step for bonding the base material A surface having the organic insulation region to the base material B surface provided with the electrode B. The step for forming an organic insulation region comprises: a step for applying a resin composition to the base material A surface provided with the electrode A to form a film having a film thickness that is at least 1.5-times the height of the electrode A; and a removal step for reducing the film thickness of the film with an organic solvent. Also provided are a bonded body, a method for producing a device, and a resin composition.

Description

Method for manufacturing a bonded body, a bonded body, a method for manufacturing a device, and a resin composition

[0001] The present invention relates to a method for manufacturing a bonded body, a method for manufacturing a bonded body, a device, and a resin composition.

[0002] Electronic devices such as mobile phones and tablet terminals are becoming increasingly smaller, while their functions are becoming more diverse. To meet these needs, electronic circuits incorporated into these devices require further miniaturization, high integration, and high-density mounting. Hybrid bonding is being considered as a method for joining electrodes in two or more semiconductor devices to achieve this miniaturization, high integration, and high-density mounting. Hybrid bonding enables high-density interconnection without the use of wires, spherical solder bumps, or underfill, and allows for fine wiring with short wiring distances. It offers various advantages such as improved electrical performance, reduced power consumption, and reduced communication delay.

[0003] For example, Non-Patent Document 1 describes a method in which a low-temperature curing polyimide material is formed on a copper pillar made using a dry film resist, smoothed by CMP polishing, and then bonded to a pattern substrate made using the same process to create a component.

[0004] Comprehensive Study on Advanced Chip on Wafer Hybrid Bonding with Copper / Polyimide Systems, 2022 IEEE 72nd Electronic Components and Technology Conference (ECTC), pp317-323

[0005] In hybrid bonding, when polyimide is used as the insulating film, a composition containing polyimide or its precursor is applied to a substrate having electrodes, the composition is cured to form a cured product, and after surface polishing, bonding is performed. Here, shortening the polishing time of the surface of the cured product is considered one of the important factors for shortening the manufacturing process time and improving productivity. Furthermore, suppressing the occurrence of voids during bonding is also important from the viewpoint of improving the insulation reliability of the product, improving yield, and improving productivity.

[0006] The present invention aims to provide a method for manufacturing a bonded body that can shorten the time required for the polishing process in the manufacturing of the bonded body and suppress the generation of voids, a bonded body manufactured by the above manufacturing method, a method for manufacturing a device including the above manufacturing method for the bonded body, and a resin composition used in the above manufacturing method for the bonded body.

[0007] Examples of typical embodiments of the present invention are shown below. <1> A method for manufacturing a bonded body comprising the steps of: preparing a base material A having a surface equipped with an electrode A; forming an organic insulating portion on the surface of the base material A equipped with the electrode A; preparing a base material B having a surface equipped with an electrode B; and joining the surface of the base material A equipped with the organic insulating portion and the surface of the base material B equipped with the electrode B, wherein the organic insulating portion forming step comprises the steps of: applying a resin composition to the surface of the base material A equipped with the electrode A to form a resin composition film having a film thickness of 1.5 times or more the height of the electrode A; and removing the resin composition film with an organic solvent to reduce the film thickness of the resin composition film. <2> The method for manufacturing a bonded body according to <1>, wherein the resin composition comprises at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. <3> A method for manufacturing a bond according to <1> or <2>, wherein electrode A contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti. <4> A method for manufacturing a bond according to any one of <1> to <3>, wherein electrode B contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti. <5> A method for manufacturing a bond according to any one of <1> to <4>, wherein in the removal step, the dissolution rate of the resin composition film in the organic solvent is 10 nm / sec or more. <6> A method for manufacturing a bond according to any one of <1> to <5>, wherein in the removal step, the dissolution rate of the resin composition film in the organic solvent is less than 200 nm / sec. <7> A method for producing a bond according to any one of <1> to <6>, wherein the dissolution rate of the resin composition film in cyclopentanone is 10 nm / sec or more and less than 200 nm / sec. <8> A method for producing a bond according to any one of <1> to <7>, wherein the content of the polymerizable compound in the resin composition is 1 to 15% by mass when the content of the resin in the resin composition is 100% by mass. <9> A method for producing a bond according to any one of <1> to <8>, wherein the resin contains a polyimide precursor containing repeating units represented by the following formula (1-1). In formula (1-1), X is a tetravalent organic group, Y is a divalent organic group, and R １ and R ２ are each independently a hydrogen atom or an organic group, and at least one of R １ and R ２ is represented by the following formula (III). In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and R ２０１ represents an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group, and * represents the bonding site with an oxygen atom. <10> The method for producing a conjugate according to <9>, wherein the polyimide precursor is a repeating unit represented by the above formula (1-1), and X in the above formula (1-1) contains a repeating unit B represented by the following formula (a) or (b). In formula (a) or formula (b), * represents the bonding site with the carbonyl group in formula (1-1). <11> The method for producing a conjugate according to any one of <1> to <8>, wherein the resin contains a polyimide having a repeating unit represented by the following formula (1-2). In formula (1-2), X １ is a tetravalent organic group, and Y １ is a divalent organic group having a group containing an ethylenic unsaturated bond. <12> A conjugate produced by the method for producing a conjugate according to any one of <1> to <11>. <13> A method for producing a device, including the method for producing a conjugate according to any one of <1> to <11>. <14> A resin composition containing at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and used in the step of forming the organic insulating portion in the method for producing a conjugate according to any one of <1> to <11>.

[0008] The present invention provides a method for manufacturing a bonded body that can shorten the time required for the polishing process in the manufacturing of the bonded body and suppress the generation of voids, a bonded body manufactured by the above manufacturing method, a method for manufacturing a device including the above manufacturing method for the bonded body, and a resin composition used in the above manufacturing method for the bonded body.

[0009] This is a schematic cross-sectional diagram illustrating a part of the process when bonding a substrate in the manufacturing method of a bonded body according to one embodiment of the present invention. This is a schematic cross-sectional diagram illustrating a part of the process when bonding a substrate in the manufacturing method of a bonded body according to one embodiment of the present invention (continuation of Figure 1). This is a schematic cross-sectional diagram illustrating a part of the process when bonding a substrate in the manufacturing method of a bonded body according to one embodiment of the present invention (continuation of Figure 2). This is a schematic cross-sectional view illustrating an example of a three-dimensional mounted semiconductor device using TSV. This is a schematic cross-sectional view showing details of the substrate used in the example. This is a schematic cross-sectional view of the test vehicle used in the bias HAST test.

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.

[0011] (Method for manufacturing a bonded body) The method for manufacturing a bonded body of the present invention includes the steps of: preparing a base material A having a surface equipped with an electrode A; forming an organic insulating portion on the surface of the base material A equipped with the electrode A; preparing a base material B having a surface equipped with an electrode B; and joining the surface of the base material A equipped with the organic insulating portion and the surface of the base material B equipped with the electrode B, wherein the organic insulating portion forming step includes the steps of: applying a resin composition to the surface of the base material A equipped with the electrode A to form a resin composition film having a film thickness of 1.5 times or more the height of the electrode A; and removing the resin composition film with an organic solvent to reduce its film thickness.

[0012] The present invention provides a method for manufacturing a bonded body that reduces the time required for the polishing process in the manufacturing of the bonded body and suppresses the generation of voids. In the manufacturing of semiconductor devices, for example, a bonded body is obtained by bonding a wafer, chips, etc., to a substrate such as a wafer. In conventional bonding methods, a resin film is formed between and on the electrodes in the substrate before bonding, and the resin film is polished with CMP or the like before bonding. The applicant believed that the time required for this polishing is relatively long, and that shortening this time would greatly improve the productivity of the process. The present invention provides a method for manufacturing a bonded body that includes the steps of forming a resin composition film whose thickness is 1.5 times or more the height of the electrodes, and a removal step of reducing the thickness of the resin composition film with an organic solvent. This removal with an organic solvent is generally considered to improve the productivity of the process because the rate of reduction of film thickness is much faster compared to polishing with CMP or the like. In addition, since polishing can be omitted or the amount of polishing can be made very small, the generation of scratches due to polishing is suppressed, and as a result, the generation of voids is also suppressed.

[0013] Non-patent document 1 neither describes nor suggests a method for manufacturing the joint of the present invention. The method for manufacturing the joint of the present invention will be described in detail below.

[0014] <Step of preparing base material A> The method for manufacturing the bonded body of the present invention includes a step of preparing a base material A having a surface equipped with electrodes A. In the step of preparing base material A, base material A may be manufactured by a known method (for example, plating on a substrate such as a silicon substrate), or it may be obtained by means of purchase or other means.

[0015] [Substrate A] Substrate A has a surface having electrode A. The form of substrate A may be a wafer or a chip, but being a wafer is one of the preferred embodiments of the present invention. In the present invention, a wafer refers to a substrate containing a semiconductor, and is a concept that includes panels formed from multiple semiconductor elements. In the present invention, a chip refers to an individual piece containing a semiconductor formed by dicing or the like, and may be a single-sided chip or a double-sided chip.

[0016] The shape of the base material A is not particularly limited, but examples include polygonal flat plates, discs, polyhedra, etc. The thickness of the base material A is preferably 0.1 to 5 mm, and more preferably 0.2 to 1 mm. The electrode A in the base material A is preferably a pillar electrode. Furthermore, the electrode A preferably contains a metal, more preferably contains 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), more preferably contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti, and even more preferably contains Cu or Sn. Examples of electrodes containing Cu or Sn include electrodes made of Cu, Sn, Sn-Ag alloy, Sn-Sb alloy, Sn-Bi alloy, etc. In this specification, the term "containing metal X" is used to collectively refer to at least one of metal X or an alloy containing that metal. Note that the alloy may contain elements other than those exemplified above. For example, a copper alloy may contain silicon atoms to form a Corson alloy. In addition, oxygen which is inevitably dissolved, and organic residues of the raw material compounds which are mixed in during precipitation, etc., may be present. The electrode A described above may be an electrode made up of multiple different components. For example, a substrate may have a portion made of a metal such as Cu, Ag, Au, or an alloy containing one or more of these (hereinafter also referred to as the "electrode portion"), and a portion made of a metal such as Ni, Sn, Pb, or an alloy containing one or more of these, which is used as solder (hereinafter also referred to as the "conducting passage"), may be formed on the electrode portion of Cu, etc., and the electrode portion and the conducting passage may be in series to form one electrode A. Among these, it is preferable that the electrode A comprises at least a member containing Cu and a member containing Sn. An example of a substrate A having a surface equipped with such an electrode A is the substrate A used in the embodiment of the present invention. In the substrate A, a guide passage made of SnAg is formed on the electrode portion made of Cu.

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

[0018] The material used for substrate A is not particularly limited and can be semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin-film transistor) array substrate, or electrode plate for plasma display panels (PDP). The substrate may have layers such as an adhesion layer or oxide layer made of hexamethyldisilazane (HMDS) on its surface. In this invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates (silicon wafers) are more preferred. Substrate A may have an electronic circuit region including an electronic circuit. The electronic circuit may also have elements such as semiconductors. Furthermore, it is preferable that the electronic circuit is electrically connected to electrode A. When substrate A is a wafer, the size can be 100 mm or more in diameter (or maximum diameter if substrate A is not circular). Furthermore, for large substrates, it is preferable that they be 200 mm or larger, and more preferably 250 mm or larger. There is no particular upper limit, but it is preferable that they be 2,000 mm or smaller. For substrate A, if it is a chip, the diameter (maximum diameter if substrate A is not circular) is preferably 7 mm or larger, more preferably 10 mm or larger, and even more preferably 20 mm or larger. As for the upper limit, it is preferable that it be 50 mm or smaller, more preferably 40 mm or smaller, and even more preferably 30 mm or smaller.

[0019] <Organic Insulation Formation Step> The method for manufacturing the bonded body of the present invention includes an organic insulation formation step in which an organic insulation portion is formed on the surface of the base material A that has the electrode A. The organic insulation portion is preferably formed to be in contact with the electrode A, and more preferably formed to fill the recess between the electrode A and the electrode A. Here, forming the organic insulation portion on the surface of the base material A that has the electrode (electrode A) means that the organic insulation portion is formed on the surface that has the electrode (electrode A), for example, another layer may be formed on the surface of the base material A and the organic insulation portion may be formed to fill the recess between the electrode A and the electrode A. That is, the surface of the base material A and the organic insulation portion do not necessarily have to be in contact, and another layer such as an adhesive layer may be formed between the surface of the base material A and the organic insulation portion. Furthermore, the organic insulation portion only needs to be formed on at least a part of the electrode A, but for example, forming it on all of the electrode A is also one of the preferred embodiments of the present invention. The organic insulation formation step preferably includes applying the resin composition to the surface of the base material A that has the electrode A and heating it. Details of application and heating will be described later.

[0020] [Organic Insulator] The organic insulating component is preferably a member containing polyimide, and may further contain components other than polyimide. Examples of components other than polyimide include components other than polyimide contained in the resin composition described later, and components that have been modified (decomposed, polymerized, structurally changed, etc.) by heating. Details of these components will be described later.

[0021] [Application Step] The organic insulating part formation step includes a step (application step) of applying the resin composition to the surface of the substrate A that has the electrode A, to form a resin composition film whose thickness is 1.5 times or more the height of the electrode A. Here, it is also preferable that the resin composition includes at least one resin selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole. Details of these resins will be described later. As described above, other layers may be formed on the surface of the substrate A, and the resin composition of the present application may be applied on top of other layers formed on the surface of the substrate A.

[0022] In the application process, the resin composition is preferably applied by coating. When the resin composition is applied by coating, it is not necessary to apply pressure to electrodes A such as pillars during application, which has the advantage of reducing the likelihood of substrate damage such as chip cracking. Examples of methods for applying the resin composition onto the substrate A include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be applied in which a coating film formed in advance on a temporary support using the above application method is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used in the present invention as well.

[0023] For example, the resin composition may be used in film form. Specifically, a resin composition containing a solvent can be applied to a film-like temporary support, and the solvent can be removed to form a resin film with a temporary support having a resin film. The resin film with the temporary support can be laminated onto a substrate A, and the temporary support can be removed to apply the resin composition to the electrode-containing surface of the substrate A. The lamination pressure is preferably 1 MPa or less, and more preferably 0.1 to 0.3 MPa. By using such a resin film with a temporary support, the process in the organic insulation part formation step is simplified, and by preparing dry films with different resin film thicknesses, it becomes easy to form resin films of the desired thickness on various substrates A. In the above resin film, the solvent content can be 5% by mass or less of the total mass of the resin film. As a method for removing the solvent, for example, a step of removing the solvent under conditions of 100°C to 150°C for 1 to 5 minutes may be carried out.

[0024] The resin film with the temporary support can be in the form of a roll that can be wound up, or in the form of a single sheet such as a rectangular shape.

[0025] As a temporary support, for example, polymer films or metal foils can be used. Polymer films are not particularly limited, but examples include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release paper such as silicone sheets, thermoplastic resin sheets with heat resistance such as fluororesins and polyimide resins. Metal foils are not particularly limited, but examples include copper or copper alloys, aluminum or aluminum alloys, iron or iron alloys, silver or silver-containing alloys, gold or gold alloys, zinc or zinc alloys, nickel or nickel alloys, tin or tin alloys. From the viewpoint of adjusting the peel strength, polyesters such as polyethylene terephthalate and polybutylene terephthalate are preferred, and polyethylene terephthalate is more preferred.

[0026] The thickness of the temporary support is not particularly limited, but may be, for example, 10 to 100 μm or 10 to 70 μm. This is preferable because it improves handling when manufacturing the resin film with the temporary support.

[0027] The resin film with temporary support may be single-layer or multi-layer, and may contain one or more types of resin films. In the case of multi-layer films, they may be composed of the same type or different types. Furthermore, the resin film with temporary support may have a protective film on the outermost layer side of the resin film.

[0028] In this embodiment, the method for forming the resin film with a temporary support is not particularly limited, but for example, a method can be used in which a varnish-like resin composition is applied to the temporary support using, for example, a comma coater, die coater, lip coater, or bar coater to form a coating film, and then the solvent is removed by appropriately drying the coating film. Among such coating methods, a comma coater may be used from the viewpoint of productivity.

[0029] Furthermore, a process to remove excess film from the edges of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing. Alternatively, a pre-wetting process may be employed in which various solvents are applied to the substrate before applying the resin composition to improve the wettability of the substrate, and then the resin composition is applied.

[0030] Furthermore, if the resin composition contains a solvent, the process may include a drying step (a drying step) in which the component made of the resin composition (hereinafter also simply referred to as "film") is dried after the resin composition is applied to the substrate A. The drying temperature in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. An example of a drying time is 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0031] The resin composition is applied and, if necessary, dried to form a resin composition film on the surface of the substrate A that has the electrode A. Here, the thickness of the resin composition film is 1.5 times or more the height of the electrode A, preferably 2.5 times or more, and more preferably 3.0 times or more. The upper limit of the above magnification is not particularly limited, but it is preferably 5.0 times or less. The thickness of the resin composition film and the height of the electrode A are measured by cross-sectional SEM (scanning electron microscope) observation. The thickness of the resin composition film is the average value of the distance from the surface on the substrate A side to the surface opposite to the substrate A in the portion of the resin composition film where the electrode A is not present. The height of the electrode A is the average value of the distance from the surface of a member other than the electrode, such as a silicon wafer on the substrate A, to the surface of the electrode A opposite to the member other than the electrode. If there are multiple electrodes A, the height of the electrode A may be the height of the smallest electrode A. Furthermore, the film thickness of the resin composition film is preferably 1.5 times or more the average height of all electrodes A, more preferably 2.5 times or more, and even more preferably 3.0 times or more. The upper limit of the above magnification is not particularly limited, but it is preferably 5.0 times or less.

[0032] From the viewpoint of shortening the process time, the dissolution rate of the resin composition film in cyclopentanone is preferably 10 nm / sec or more, more preferably 50 nm / sec or more, and even more preferably 100 nm / sec or more. From the viewpoint of reliability, the above dissolution rate is preferably 500 nm / sec or less, more preferably 300 nm / sec or less, and even more preferably 200 nm / sec or less. The above dissolution rate is calculated by immersing a substrate A having the resin composition film in cyclopentanone and measuring the decrease in film thickness using a film thickness measuring instrument.

[0033] [Removal Step] The organic insulating part formation step includes a removal step in which the film thickness of the resin composition film is reduced using an organic solvent. In the removal step, the film thickness of the resin composition film may be reduced overall, or it may be reduced in part.

[0034] -Organic Solvents- Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, alkyloxyethyl acetate, alkyloxybutyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)). ), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate) (For example, methyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.) , and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate,Suitable examples include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, anisole, and limonene, and sulfoxides such as dimethyl sulfoxide.

[0035] In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred as the organic solvent, and cyclopentanone is more preferred. One or more organic solvents may be used as a mixture. The organic solvent may further contain other components. Examples of other components include water, known surfactants, and known defoaming agents. The content of these other components is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100 parts by mass of the organic solvent.

[0036] -Method of supplying organic solvent- The method of supplying the organic solvent is not particularly limited as long as it can reduce the film thickness of the resin composition film, and can be a method of immersing the substrate A in the organic solvent, a method of supplying the organic solvent onto the substrate A using a nozzle and removing it with a paddle, or a method of continuously supplying the organic solvent. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of the penetration and removal of the organic solvent and the efficiency of manufacturing, the method of supplying the organic solvent with a straight nozzle or the method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of the penetration of the organic solvent, the method of supplying it with a spray nozzle is more preferred. Alternatively, after continuously supplying the organic solvent with a straight nozzle, the substrate may be spun to remove the organic solvent from the substrate A, and after spin drying, the organic solvent may be supplied again with a straight nozzle, and the substrate A may be spun to remove the organic solvent from the substrate A, and this process may be repeated multiple times. Furthermore, possible methods for supplying the organic solvent include a process in which the organic solvent is continuously supplied to the substrate A, a process in which the organic solvent is kept in a nearly static state on the substrate A, a process in which the organic solvent is vibrated on the substrate A using ultrasound or the like, and a process that combines these methods.

[0037] The removal time is preferably 5 seconds to 10 minutes, and more preferably 10 seconds to 5 minutes. The temperature of the organic solvent is not particularly specified, but it can usually be carried out at 10 to 45°C, preferably 20 to 40°C.

[0038] After treatment with an organic solvent, rinsing may be performed further. Alternatively, methods such as supplying the rinsing solution before the organic solvent in contact with the resin composition film has completely dried may be employed. It is preferable to use an organic solvent different from the one used to remove the resin composition film for rinsing. Examples of rinsing solutions include PGMEA (propylene glycol monomethyl ether acetate) and IPA (isopropanol), with PGMEA being preferred. When the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. 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 more preferred, and cyclohexanone and PGMEA are even more preferred.

[0039] If the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of the organic solvent, more preferably 70% or more by mass of the organic solvent, and even more preferably 90% or more by mass of the organic solvent. Alternatively, the rinsing solution may contain 100% by mass of the organic solvent.

[0040] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0041] -Method of supplying the rinsing solution- The method of supplying the rinsing solution is not particularly limited, and the same method as for the organic solvent described above can be used.

[0042] - Dissolution Rate - In the removal process, the dissolution rate of the resin composition film in the organic solvent is preferably 10 nm / sec or more, more preferably 50 nm / sec or more, and even more preferably 100 nm / sec or more, from the viewpoint of shortening the process time. From the viewpoint of reliability, the dissolution rate is preferably 500 nm / sec or less, more preferably 300 nm / sec or less, and even more preferably 200 nm / sec or less. The dissolution rate is calculated by measuring the amount of film thickness reduction in the removal process using a film thickness measuring instrument.

[0043] -Removal Amount- The amount of reduction in the thickness of the resin composition film during the removal process is not particularly limited, but it is preferably an amount that reduces the thickness of the resin composition on electrode A to 200 nm or less, more preferably to 100 nm or less, and even more preferably to 50 nm or less. The lower limit is not particularly limited and may be an amount that reduces the thickness of the resin composition on electrode A to 0 nm. The above reduction amount is preferably, for example, 5 to 50 μm, and more preferably to 10 to 30 μm.

[0044] [Patterning step] The organic insulating part formation step may include a patterning step of the resin composition film. If a resin composition containing a photosensitive compound such as a photopolymerization initiator described later is used, this patterning can be carried out by exposure and development. The patterning step is preferably performed after the application step described above and before the removal step described above.

[0045] - Exposure Step - In the organic insulating part formation step, the resin composition film may be subjected to an exposure step in which the film is selectively exposed. That is, the method for manufacturing the bonded body of the present invention may include an exposure step in which the film formed by the application step is selectively exposed in the organic insulating part formation step. Selective exposure means exposing a part of the organic insulating part. Furthermore, by selective exposure, an exposed area (exposed area) and an unexposed area (unexposed area) are formed in the organic insulating part. Details of the exposure step, such as exposure means and exposure conditions, can be found in paragraphs 0027 to 0029 of Japanese Patent Application Publication No. 2023-178289. The above description is incorporated herein by reference.

[0046] -Post-exposure heating step- The film subjected to the exposure step may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for manufacturing the bonded body of the present invention may include a post-exposure heating step in which the organic insulating portion exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. For details of the post-exposure heating step, refer to paragraph 0030 of Japanese Patent Application Publication No. 2023-178289. The above description is incorporated herein by reference.

[0047] -Development Process- The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a bonded body of the present invention may include a development process in the organic insulating part formation process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the organic insulating part is removed by the development process is called negative development, and development in which the exposed part of the organic insulating part is removed by the development process is called positive development. By performing exposure development, for example, it is possible to remove the resin composition from the parts that are cut during dicing (dicing lines). According to such an embodiment, for example, it is possible to prevent foreign matter contamination due to resin peeling during dicing. As a result, the yield in the manufacture of the bonded body can be improved. For details of the development process, such as the developer, development method, and development conditions, refer to paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2023-178289. The above description is incorporated herein by reference.

[0048] [Heating Step] The organic insulating part formation step is preferably subjected to a heating step in which the resin composition film is heated after the removal step described above. That is, the organic insulating part formation step may include a heating step in which the resin composition film is heated. For example, this could be an embodiment in which the resin composition film is heated after the removal step, or an embodiment in which the patterned film is heated after the application step, exposure step, development step and removal step. In the heating step, some of the structures contained in the specific resin described later may be further cyclized. In addition, crosslinking of crosslinkable groups in the specific resin or crosslinking agents other than the specific resin may also proceed. The heating temperature (maximum heating temperature) in the heating step is preferably 250°C or less, more preferably 220°C or less, even more preferably 200°C or less, and can also be 180°C or less. The lower limit of the above heating temperature is preferably 160°C or higher, and more preferably 170°C or higher.

[0049] The heating step is preferably a step in which heating promotes the polymerization of polymerizable groups in the organic insulating portion. Alternatively, the heating step may be a step in which heating promotes the cyclization reaction of a specific resin.

[0050] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

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

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

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

[0054] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, in order to prevent the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0055] [Post-exposure step] The organic insulating portion obtained by the organic insulating portion formation step may be subjected to a post-exposure step to expose the organic insulating portion, either in place of the heating step or in addition to the heating step. That is, the method for manufacturing the bonded body of the present invention may include a post-exposure step to expose the organic insulating portion. The method for manufacturing the bonded body of the present invention may include a heating step and a post-exposure step, or it may include only one of the heating step and the post-exposure step. In the post-exposure step, for example, a reaction in which cyclization of polyimide, etc., proceeds by photosensitization of the photobase generator can be promoted. In the post-exposure step, it is sufficient for at least a part of the organic insulating portion to be exposed, but it is preferable for the entire organic insulating portion to be exposed. The amount of exposure in the post-exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２Preferably, the concentration is 100 to 15,000 mJ / cm². ２ It is more preferable that this is the case. The post-exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0056] [Formation in Two or More Layers] In the organic insulating part formation process, forming the organic insulating part in two or more layers is also one of the preferred embodiments of the present invention. That is, the organic insulating part may have a structure in which multiple layers made of a resin composition are laminated. However, in the formation of the second layer, a part of the first layer may dissolve in the solvent, and the interface between these layers may not be clear. By forming the organic insulating part in two or more layers, the flatness of the surface of the organic insulating part is improved, which has advantages such as making it easier to perform the planarization process described later. In the above embodiment, the organic insulating part is preferably formed in two to four layers, more preferably in two or three layers, and even more preferably in two layers. When forming the organic insulating part in two or more layers, examples include performing the application process (and a drying process if necessary) consecutively, followed by the heating process described above, or repeating the application process (and a drying process if necessary) and the heating process multiple times. Alternatively, for example, the application process (and a drying process if necessary) may be performed consecutively, followed by the exposure process, post-exposure heating process, and development process described above, and then the heating process described above. Furthermore, after performing the above-described application step, and optionally the exposure step, post-exposure heating step, and development step, the above-described heating step may be performed to form the first layer, and then the above-described application step, and optionally the exposure step, post-exposure heating step, and development step may be performed on the first layer, and then the above-described heating step may be performed to form the second and subsequent layers. Moreover, when performing the application step to heating step on the first layer, the conditions of the exposure step, heating step, etc., which are performed as needed, may be adjusted to a semi-cured state, and then the application step to heating step for the second and subsequent layers may be performed further. In addition, when forming the organic insulating part with two or more layers, the components contained in the resin composition used to form each layer and the content ratio of each component may be the same or different.

[0057] <Step of preparing base material B> The method for manufacturing the bonded body of the present invention includes the step of preparing a base material B having a surface equipped with an electrode B.

[0058] The form of substrate B may be a wafer or a chip. These can be selected according to the desired design of the bonded structure.

[0059] [Base material B] Base material B has an electrode B. The thickness of base material B is preferably 0.1 to 5 mm, and more preferably 0.2 to 1 mm. In the bonded body obtained by the bonding process described later, it is preferable that at least a part of the electrode B is electrically bonded to the electrode A in base material A.

[0060] The material used for substrate B is not particularly limited, but the same material as that used for substrate A described above is preferred. The preferred embodiment of electrode B is the same as the preferred embodiment of electrode A. Substrate B may have an electronic circuit region including an electronic circuit. The electronic circuit may have elements such as semiconductors. It is also preferable that the electronic circuit is electrically connected to the electrode. When substrate B is a wafer, the diameter (maximum diameter if substrate B is not circular) can be 100 mm or more. For larger substrates, for example, it is preferable to be 200 mm or more, and more preferably 250 mm or more. There is no particular upper limit, but it is preferable to be 2,000 mm or less. When substrate B is a chip, the diameter (maximum diameter if substrate B is not circular) is preferably 7 mm or more, more preferably 8 mm or more, and even more preferably 10 mm or more. As an upper limit, for example, it is preferable to be 50 mm or less, more preferably 30 mm or less, and even more preferably 20 mm or less.

[0061] Furthermore, it is preferable that the substrate B includes an inorganic insulating film between the electrodes. The inorganic insulating film is not particularly limited, but examples include silicon oxide film, silicon nitride film, silicon oxynitride film (the ratio of oxygen to nitrogen content is not particularly limited), aluminum oxide film, aluminum nitride film, hafnium oxide film, yttrium oxide film, zirconium oxide film, gallium oxide film, tantalum oxide film, magnesium oxide film, lanthanum oxide film, cerium oxide film, neodymium oxide film, silicon carbon nitride (SiCN) film, etc. It is preferable that the inorganic insulating film insulates the multiple electrodes included in electrode B. Furthermore, if the substrate B includes an inorganic insulating film, the second organic insulating part formation step described later may be performed, but it is also possible to omit the second organic insulating part formation step.

[0062] <Second Organic Insulation Formation Step> The method for manufacturing the bonded body of the present invention further includes a second organic insulation formation step of forming a second organic insulation on the surface of the base material B equipped with the electrode B, and it is preferable that the second organic insulation formation step and the bonding step are included in this order. The second organic insulation formation step can be carried out, for example, by the same method as the organic insulation formation step for the base material A described above. Alternatively, other known methods may be used. Here, in the second organic insulation formation step, a resin composition may be used, or another known composition for forming an organic insulation may be used, but it is preferable to use a resin composition. However, when a resin composition is used in the second organic insulation formation step, the composition of the resin composition used in the second organic insulation formation step and the composition of the resin composition used in the organic insulation formation step for the base material A may be the same or different. The preferred embodiment of the second organic insulation is the same as the preferred embodiment of the organic insulation formed on the base material A described above. In the joining process described later, it is believed that the adhesion of the joined body is improved by joining the second organic insulating portion and the organic insulating portion formed on the base material A described above in contact at least in part.

[0063] <Planarization Step> The method for manufacturing the bonded body of the present invention further includes a planarization step of planarizing the surface of the organic insulating portion of the base material A, and the organic insulating portion forming step, the planarization step, and the bonding step may be included in this order. In the bonding step described later, it is preferable that the planarized organic insulating portion on the base material A and the surface of the base material B (or the surface of a second organic insulating portion which may be planarized) are joined in contact.

[0064] As a result of the planarization described above, it is preferable that the electrode A on the substrate A is exposed from the organic insulating portion. Furthermore, in the substrate A and the organic insulating portion after the planarization, the electrode A and the organic insulating portion may be at the same height, the electrode A may be recessed relative to the organic insulating portion, or the organic insulating portion may be recessed relative to the electrode A. Here, the difference in height between the electrode A and the organic insulating portion after planarization is preferably ±1 μm or less, and more preferably ±0.5 μm or less. The planarization may be performed by physical polishing such as cutting, mechanical polishing, grinding, plasma treatment, or laser ablation, or by chemical polishing such as CMP (Chemical Mechanical Polishing). The polishing rate of the organic insulating portion during the planarization is preferably 100 nm / min or more, more preferably 200 nm / min or more, and even more preferably 400 nm / min or more. There is no particular upper limit to the polishing rate, but from the viewpoint of controlling the in-plane uniformity of the polished object, it is preferable to have a rate of less than 3000 nm / min. The polishing rate of electrode A on substrate A during the planarization process is preferably less than or equal to the polishing rate of the organic insulating portion, and more preferably less than or equal to half the polishing rate of the organic insulating portion. The slurry used in the CMP is not particularly limited, but silica slurry, ceria slurry, alumina slurry, etc., can be used. For example, alumina slurry is preferred from the viewpoint of flatness and polishing speed, and silica slurry is preferred from the viewpoint of polishing speed. The particle size of the slurry is not particularly limited, but from the viewpoint of suppressing scratches, an average particle size of 1000 nm or less is preferred, an average particle size of 500 nm or less is more preferred, and an average particle size of 200 nm or less is even more preferred. The lower limit of the particle size of the slurry is not particularly limited, but from the viewpoint of polishing rate, it is preferably 10 nm or more.

[0065] [TTV] In the planarization process, it is preferable that the organic insulating portion is planarized together with electrode A. The degree of planarization is preferably such that the TTV (Total Thickness Variation) of the organic insulating portion and electrode A is 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. In this invention, TTV refers to the arithmetic mean of the film thickness differences (T1-T2) of the remaining sections. The TTV is calculated by dividing the area 1 mm or more inward from the edge of the organic insulating part into 2 mm square sections (if the area of ​​the organic insulating part is too small to be divided into 2 mm square sections, the entire area 1 mm or more inward from the edge of the organic insulating part is considered one section), measuring the maximum thickness (T1) and the minimum thickness (T2) between one surface and the other surface for each section, calculating the film thickness difference (T1-T2) for each section, assigning a hierarchy to the sections in descending order of film thickness difference (T1-T2), excluding a number of section groups corresponding to 10% of the total number of sections (rounded down if decimal places exist) in descending order of film thickness difference starting from the top-ranked section (largest film thickness difference), and excluding a number of section groups corresponding to 10% of the total number of sections (rounded down if decimal places exist) in descending order of film thickness difference starting from the lowest-ranked section (smallest film thickness difference), and so on. In this specification, the term "section evaluation TTV" may be used when referring specifically to the TTV of the organic insulating portion as defined herein. By setting the TTV of the organic insulating portion to below the above upper limit, the film thickness becomes generally uniform, and the adhesion to the substrate B is improved.

[0066] [Ra] The organic insulating portion of the present invention preferably has a surface roughness Ra of 10 nm or more and 1.5 μm or less on the side opposite to the side in contact with the surface of the substrate A. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, even more preferably 300 nm or less, even more preferably 200 nm or less, even more preferably 150 nm or less, and even more preferably 120 nm or less. By setting the surface roughness of the organic insulating portion to be above the lower limit, an anchoring effect can be activated to improve adhesion with the substrate B. Furthermore, by setting the surface roughness to be below the upper limit, the occurrence of defects such as voids due to the inclusion of bubbles during bonding with the substrate B can be effectively suppressed.

[0067] When forming a second organic insulating portion on substrate B, it is preferable to include a second planarization step between the second organic insulating portion formation step and the joining step, in which the surface of the second organic insulating portion is planarized. The second planarization step can be carried out in the same manner as the planarization step for substrate A described above.

[0068] <Joining Process> The method for manufacturing a joined body of the present invention includes a joining process of joining the surface of the base material A having an organic insulating portion and the surface of the base material B having the electrode B. If the base material B has a second organic insulating portion, the joining process is a process of joining the surface of the base material A having an organic insulating portion and the surface of the base material B having the second organic insulating portion.

[0069] Through bonding, electrode A on substrate A and electrode B on substrate B are electrically joined. In the bonding process, it is also a preferred embodiment of the present invention that the electrode included in the surface of substrate A having an organic insulating portion and the electrode on the surface of substrate B having electrode B are joined in direct contact. That is, it is also preferable that neither electrode A nor electrode B has a conductive path.

[0070] The joining is preferably carried out by means including heating, and more preferably by means including heating and pressurizing. The joining temperature is preferably 100°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. The upper limit is preferably 450°C or lower, more preferably 400°C or lower, even more preferably 380°C or lower, particularly preferably 350°C or lower, even more preferably 300°C or lower, even more preferably 280°C or lower, even more preferably 260°C or lower, and even more preferably 250°C or lower. This temperature is preferably near the melting point of the conduit, taking into consideration the need to melt the conduit and enable joining between electrodes, as described above. The heating time in the joining process is not particularly limited, but is preferably 5 seconds or more, more preferably 1 minute or more, and even more preferably 2 minutes or more. The upper limit is practically 30 minutes or less. The heating environment is not particularly limited, but is preferably carried out under a reduced pressure atmosphere while mechanically pressurizing the organic insulating part. The atmospheric pressure is 1 x 10 －５ It is preferable that it be 1 × 10⁻¹⁰ mbar or higher. －４ It is more preferable that it be 5 × 10 mbar or higher. －４ It is even more preferable that it be 0 mbar or higher. Preferably, the upper limit is 0.1 mbar or less, and 1 × 10 －２ It is more preferable that it be less than or equal to mbar, and 5 × 10 －３ It is even more preferable that the pressure be less than or equal to mbar. In this specification, 1 bar is equal to 100 kPa. Bonding is preferably performed by sandwiching two substrates (substrate A and substrate B), and it is preferable to apply pressure to the substrates at this time. The pressure applied to the substrates is preferably 1 kN or more, more preferably 5 kN or more, and even more preferably 10 kN or more. As an upper limit, it is practical to be 100 kN or less. The apparatus used in the bonding process is not particularly limited, but apparatus used for reflow of electronic components can be suitably used.

[0071] Furthermore, in the bonding process, it is preferable that the temperature of the substrate A equipped with the organic insulating portion is preheated to 70°C or higher. Also, if the substrate B includes a second organic insulating portion, it is preferable that the temperature of the substrate B is preheated to 70°C or higher. The above temperature is preferably 70°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit of the above temperature is not particularly limited, but it is preferably 130°C or lower. With the above embodiment, the cycle time of the bonding process can be reduced. In addition, the fluidity of the organic insulating portion during bonding may be improved, and the maximum peel resistance may also be improved.

[0072] The thermal diffusivity of the organic insulation part after the bonding process is 2.0 × 10⁻⁶. －７ I understand ２ s －１ Preferably, it is 3.0 × 10 －７ I understand ２ s －１ It is more preferable that the above be the case, 5.0 × 10 －７ I understand ２ s －１ The above is even more preferable. The thermal diffusivity of the organic insulating part after the bonding process can be adjusted by designing, for example, the type of material of the filler, the particle size of the filler (combination of particle sizes if two or more types of 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, if the organic insulating part after the bonding process contains a filler. Fillers will be described later.

[0073] The organic insulating portion after the joining process is preferably an insulating material. The insulating properties (electrical resistance) of the organic insulating portion after the joining process are not particularly limited, but the volume resistivity is 1 × 10⁻⁶. １５ It is preferable that it be Ω·cm or more, and 1 × 10 １６ It is more preferable that it be Ω·cm or greater. There is no particular upper limit, but 1 × 10 １９It is practical for the volume resistivity to be Ω·cm or less. The dielectric breakdown voltage is preferably 1 kV / mm or more, and more preferably 10 kV / mm or more. There is no particular upper limit, but it is practical for it to be 1000 kV / mm or less. In this specification, the measurement of volume resistivity and dielectric breakdown voltage shall be in accordance with JIS C2151:2006 and JIS C2318:2007.

[0074] Furthermore, the glass transition temperature of the organic insulating portion after the bonding process is preferably 250°C or lower, more preferably 230°C or lower, and even more preferably 220°C or lower. The lower limit of the above glass transition temperature is not particularly limited, but it is preferably 120°C or higher.

[0075] The preferred embodiments of the thermal diffusivity, volume resistivity, dielectric breakdown voltage, and glass transition temperature of the second organic insulating portion after the bonding process are the same as those preferred embodiments of the organic insulating portion after the bonding process described above.

[0076] The cyclization rate of polyimide in the above organic insulating part formation process (i.e., the cyclization rate after the heating process if a heating process is included) is preferably 90% or more, more preferably 92% or more, and even more preferably 95% or more. The upper limit of the above imidization rate is not particularly limited and may be 100% or less. The cyclization rate of polyimide in the organic insulating part formed at the above joint after the bonding process is preferably 91 to 100%, more preferably 94 to 100%, and even more preferably 97 to 100%. In the present invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents may include solvents contained in the resin composition, such as NMP. The viscosity may also be changed as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 110°C for 5 minutes to obtain a uniform resin layer with a thickness of approximately 15 μm on the silicon wafer. If only a resin solution with low viscosity is available, making it difficult to obtain a resin layer with a thickness of 15 μm, the thickness may be adjusted accordingly. For example, if the thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer is measured using the ATR method with a Nicoleti S20 (Thermofisher), within a measurement range of 4000–700 cm². －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the highest peak intensity (if there are multiple peaks). For a film heated at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min, the imidization index B is calculated using the same method, and the imidization rate of the resin is calculated by dividing the imidization index A by the imidization index B.

[0077] <Annealing Process> The annealing process is a heating process that may be incorporated after the bonding process (for example, bonding by a flip-chip bonder). The annealing process can increase the peel resistance of the bonded portion. The heating means are not particularly limited, but heating equipment such as a hot plate or oven can be used. The heating temperature in the annealing process is preferably lower than or equal to the bonding temperature in the bonding process. The heating temperature in the annealing process is preferably 180 to 440°C, more preferably 200 to 350°C, and even more preferably 210 to 260°C. The heating temperature in the annealing process may also be determined by considering the bonding temperature in the bonding process and the heating temperature in the heating process. The difference between the bonding temperature in the bonding process and the heating temperature in the annealing process (bonding temperature in the bonding process - heating temperature in the annealing process) is preferably 10°C or more. There is no particular upper limit, but for example, it is preferably 250°C or less, and more preferably 200°C or less. When performing the above heating process, the heating temperature in the annealing process is preferably higher than or equal to the heating temperature (maximum heating temperature) in the above heating process. The difference between the heating temperature in the annealing process and the heating temperature in the bonding process (heating temperature in the annealing process - heating temperature in the bonding process) is preferably 10°C or more, and more preferably 30°C or more. There is no particular upper limit, but for example, it is preferably 250°C or less, and more preferably 150°C or less. Furthermore, the heating time in the annealing process is preferably longer than or equal to the bonding time in the bonding process. The heating time in the annealing process (heating time at the above heating temperature) is preferably 1 hour or more. There is no particular upper limit to the above heating time, but it is preferably 10 hours or less, and more preferably 5 hours or less. The difference between the heating time in the annealing process and the heating time in the bonding process (heating time in the annealing process - heating time in the bonding process) is preferably 30 minutes or more. There is no particular upper limit, but it is preferably 10 hours or less, and more preferably 5 hours or less. The atmosphere during heating is under Air, N ２The heating equipment can be appropriately selected from available options, such as under vacuum or below. The ambient pressure is not particularly limited, but it is preferable to carry it out at 1 atmosphere or less, and more preferably within 1 atmosphere ± 0.1 atmosphere. 1 atmosphere is defined as 101,325 Pa. For example, it can be carried out at atmospheric pressure without any special pressurization or depressurization. The imidization rate after the annealing process is preferably, for example, 98% or more. The upper limit is not particularly limited, and it is also preferable for it to be, for example, 100%.

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

[0079] <Example of a Method for Manufacturing a Joined Body> Below, an example of a method for manufacturing a joined body will be explained with reference to the figures. Figure 1 is a schematic cross-sectional diagram illustrating a part of the process when bonding a substrate in a method for manufacturing a joined body according to one embodiment of the present invention. First, a substrate A (base substrate) 1 is prepared in which an electronic circuit region 8 is arranged on a silicon wafer 1x and an electrode 31 (electrode A) is attached thereto (Figure 1(a)). An electronic circuit 81 composed of a conductor or semiconductor has already been formed inside the electronic circuit region 8 of the substrate A1. The method for forming the electronic circuit is not particularly limited and can be formed by conventional methods. Furthermore, the structure and components of the electronic circuit are not particularly limited, and examples include a transistor and a wiring structure that connects it to the electrode.

[0080] A resin composition is applied to the electrode-placed surface (surface having an electronic circuit region) P0 of the substrate A1 to form a component (resin composition film) 4 made of the resin composition (Figure 1(b)). In this state, the resin composition film may be heated and dried (drying step). Here, the film thickness d1 of the resin composition film 4 is 1.5 times or more the height d2 of the electrode A. After drying, the resin composition layer 4 may be patterned by photolithography or ion sputtering.

[0081] Subsequently, in this embodiment, the film thickness of the resin composition layer 4 is reduced with an organic solvent. Then, heating is performed to promote polymerization and, if necessary, cyclization, to cure the polyimide into an organic insulating part 41 (Figure 1(c)). This forms an organic insulating part-distributed substrate 1y on which the organic insulating part 41 is disposed on the substrate A1. In addition, although the substrate A shown in the figure has only an electrode 31 as electrode A, a guide channel may be formed on the electrode 31. The guide channel may be formed on the substrate A from the beginning, or the organic insulating part may be patterned before curing, and the guide channel may be created on the patterned part by plating or other means.

[0082] Figures 2(a) to 2(c) show the substrate (laminated structure) 1z with the organic insulating portion after flattening. The tip 31a of the electrode 31 is exposed on the surface 4b of the organic insulating portion, and the entire surface 4b of the organic insulating portion is flattened. Figure 2(a) shows an example where the height of the electrode 31 and the height of the surface 4b of the organic insulating portion are the same, Figure 2(b) shows an example where the height of the surface 4b of the organic insulating portion is lower than the height of the electrode 31, and Figure 2(c) shows an example where the height of the surface 4b of the organic insulating portion is higher than the height of the electrode 31.

[0083] A substrate B is prepared separately for the laminate (a substrate with a planarized organic insulating portion) 1z (Figure 3(a)). The substrate B2 comprises a silicon wafer 2x having through-hole electrodes 2y, a circuit wiring region 8 having circuit wiring 81 arranged thereon, and electrodes 32 (electrodes B) formed within the circuit wiring region 8. In this embodiment, a second organic insulating portion 42 is also formed on the surface of the substrate B having electrodes B, and its surface 2a is planarized in the same way as the surface of the organic insulating portion 41 on the substrate A. The formation and planarization of the second organic insulating portion 42 can be carried out in the same way as the formation and planarization of the organic insulating portion 41. In this way, because the surfaces of the organic insulating portion 41 and electrodes 31 of the substrate A and the surfaces of the second organic insulating portion 42 and electrodes 32 of the substrate B are both planarized, electrical connectivity is improved even when there are no conductive passages as in the embodiment shown in this figure. At this time, the electrode 31 portion of the laminate and the electrode 32 provided on the substrate B2 are aligned (positioned) so that they come into contact. Here, if at least one of the organic insulating portion 41 and the second organic insulating portion 42 contains a migration inhibitor, even if misalignment occurs in this alignment, the migration of metal from the electrode 31 (electrode 32) to the organic insulating portion 41 (second organic insulating portion 42) can be suppressed, and the dielectric strength can be improved. In the case of electrode B, a conductive passage may also be formed on electrode 32. The conductive passage may be formed in the substrate B from the beginning, or the second organic insulating portion may be patterned before hardening, and the conductive passage may be created in the patterned portion by plating or the like.

[0084] Next, in this embodiment, the aligned substrate B2 and the laminate 1z are joined by contacting them at the joining surface P1 via the organic insulating portion 41 and the second organic insulating portion 42 (Figure 3(b)). This forms a joined body 100 in which two substrates are joined. In the joined body 100, the electrode 31 and the electrode 32 are electrically joined (joining process). At the same time, the organic insulating portion 41 is softened by heating, and the surface 4b of the organic insulating portion of the laminate 1z and the surface 2a of the substrate B (the flattened surface of the second organic insulating portion 42) are bonded together to form the joined body 100. In the joined body 100, an organic insulating portion 51 is formed from the organic insulating portion 41 and the second organic insulating portion 42, including the organic insulating portion after the joining process and the second organic insulating portion after the joining process.

[0085] (Resin Composition) The following describes preferred embodiments of the resin composition used in the application process described above.

[0086] <Specific Resin> The resin composition contains at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. In the present invention, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure are more preferred. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. That is, the resin composition preferably contains at least one resin selected from the group consisting of polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyamideimide, and polyamideimide precursors as the specific resin. The resin composition preferably contains polyimide or a polyimide precursor as a specific resin. The specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If the specific resin has radical polymerizable groups, the resin composition preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition. The specific resin may also have polarity-converting groups such as acid-degradable groups. If the specific resin has acid-degradable groups, the resin composition preferably contains a photoacid generator. For example, a chemically amplified positive-type or negative-type photosensitive film can be formed from such a resin composition.

[0087] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2). In formula (2), A １ and A ２Each is independently an oxygen atom or -NR ｚ - represents R １１１ R represents a divalent organic group. １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ｚ represents a hydrogen atom or a monovalent organic group.

[0088] A in equation (2) １ and A ２ Each is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. １１１ R represents a divalent organic group. １１１ It is preferable that the base is one of the bases described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421.

[0089] Also, R １１１ From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). In formula (61), R ５８ and R ５９Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0090] R in equation (2) １１５ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure. In formula (5), R １１２ The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ It is more preferable that the group is selected from -CH ２ -, -C (CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0091] R １１５ Preferably, this is a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Publication No. 2023-003421.

[0092] In equation (2), R １１１ and R １１５It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0093] R in equation (2) １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４ It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0094]

[0095] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２- represents a cycloalkylene group or a polyalkylene oxy group. Preferred R ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２-, cyclohexyl groups, polyalkylene oxy groups are more preferred, alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0096] In equation (2), R １１３When it is a hydrogen atom, or R １１４ When it is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0097] In formula (2), R １１３ and R １１４ At least one of may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

[0098] In particular, the polyimide precursor preferably contains a repeating unit represented by the following formula (1-1). The repeating unit represented by formula (1-1) is a preferred embodiment of the repeating unit represented by formula (2). In formula (1-1), X is a tetravalent organic group, Y is a divalent organic group, and R １ and R ２ are each independently a hydrogen atom or an organic group, and at least one of R １ and R ２ is represented by the following formula (III). In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and R ２０１ represents an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２- represents a cycloalkylene group or polyalkylene oxy group, and * represents a bond site with an oxygen atom.

[0099] In formula (1-1), X, Y, R １ and R ２ A preferred embodiment is R in formula (2) described above. １１５ , R １１１ , R １１３ and R １１４ This is similar to the preferred embodiment of [formula]. Furthermore, the preferred embodiment of formula (III) is as described above.

[0100] Here, the polyimide precursor is preferably a repeating unit represented by the above formula (1-1), wherein X in the above formula (1-1) contains a repeating unit B represented by the following formula (a) or (b). In formula (a) or formula (b), * represents the bonding site with the carbonyl group in formula (1-1).

[0101] The polyimide precursor may also preferably contain fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0102] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0103] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude. Formula (2-A) In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ Each of these independently represents a divalent organic group, R１１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R １１３ and R １１４ Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0104] A １ A ２ , R １１１ , R １１３ and R １１４ These are, independently of A in equation (2), １ A ２ , R １１１ , R １１３ and R １１４ This is synonymous with the following, and the preferred range is also similar. １１２ R in equation (5) is １１２ This is synonymous with the same thing, and the preferred range is also similar.

[0105] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2), the polyimide precursor may also contain other types of repeating units.

[0106] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0107] The imidization rate (also called the "ring closure rate") of the polyimide precursor is preferably less than 70%, more preferably 50% or less, even more preferably 30% or less, and particularly preferably 20% or less, from the viewpoint of the film strength and insulating properties of the resulting organic film. The lower limit of the above imidization rate is not particularly limited and may be 0% or more.

[0108] In this invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents that can be used include solvents contained in the resin composition, such as NMP. The viscosity may also be changed as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. Here, if only a resin solution with low viscosity can be obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be changed as appropriate. For example, if the film thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer was measured using the ATR method with Nicoleti S20 (manufactured by Thermofisher), with a measurement range of 4000-700 cm. －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１ The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the maximum peak intensity (if there are multiple peaks) and heating the film at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min. The imidization index B is calculated in the same manner and the value obtained by dividing the imidization index A by the imidization index B is calculated as the imidization rate of the resin. In measuring the imidization rate, the resin to be measured for imidization rate can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and crystallized to precipitate the resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours to obtain the resin.

[0109] 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) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When a resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0110] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, but it is preferable that it is a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide means a polyimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium, and from the viewpoint of pattern formation, it is preferable that it is a polyimide that dissolves at a rate of 0.5 g or more, and more preferably a polyimide that dissolves at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferable that it is 100 g or less. From the viewpoint of film strength and insulating properties of the resulting organic film, it is preferable that the polyimide is a polyimide having multiple imide structures in its main chain.

[0111] -Fluorine Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have fluorine atoms. Fluorine atoms are, for example, in the R of the repeating unit represented by formula (4) described later. １３２, or R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0112] -Silicon Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３１ It is more preferable that the silicon atoms or the organically modified (poly)siloxane structure described later be included. The silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and preferably 20% by mass or less.

[0113] - Ethylene-unsaturated bond - From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in the side chains, but it is preferable that it has one in the side chains. It is preferable that the above ethylenically unsaturated bond has radical polymerizability.

[0114] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0115] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in the following. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0116] -Polarity-Converting Group- Polyimides may have polarity-converting groups such as acid-degradable groups. The acid-degradable group in polyimides is R in formula (2) above. １１３ and R １１４ The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity-converting group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found at the ends of polyimides, etc.

[0117] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. The above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. When polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development"), 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 above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid groups contained in polyimides are preferably acid groups with a pKa of 0 to 10, and more preferably acid groups with a pKa of 3 to 8. pKa is the negative common logarithm of the equilibrium constant Ka, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The value of pKa may also be referenced from the value published in the "Revised 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such acid groups, polyimides preferably contain at least one selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contain phenolic hydroxyl groups.

[0118] -Phenolenic Hydroxyl Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. １３２ or R １３１It is preferable that it be included in [the polyimide]. The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0119] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4). In formula (4), R １３１ R represents a divalent organic group. １３２ R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) In formula (4-1), R １３３ This is a polymerizable group, and the other groups are equivalent to those in formula (4). Formula (4-2) In formula (4-2), R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0120] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. １３１ R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is １１１ Similar examples are given, and the preferred range is also similar. １３１ Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. １１１ Examples include:

[0121] R １３１It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0122] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0123] R １３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５ Similar examples are given, and the preferred range is also similar. For example, R １１５ The four bonders of the tetravalent organic group, as exemplified, bond with the four -C(=O)- parts in formula (4) to form a fused ring.

[0124] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor. １１５ Examples include: From the standpoint of the strength of the organic film, R １３２ It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0125] R １３１ and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１As examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples, R １３２ As such, (DAA-1) to (DAA-5) above can be cited as more preferred examples.

[0126] Furthermore, it is preferable that the polyimide has repeating units represented by the following formula (1-2). The repeating unit represented by formula (1-1) is a preferred embodiment of the repeating unit represented by formula (4). In formula (1-2), X １ Y is a tetravalent organic group, １ X is a divalent organic group having a group containing an ethylenically unsaturated bond. In formula (1-2), X １ A preferred embodiment is X in formula (1-1) described above. １ This is similar to the preferred embodiment. In formula (1-2), Y １ It is preferable that the structure includes a group represented by formula (Y-1), and more preferably that it is a structure represented by formula (Y-1). In formula (Y-1), R １ and R ２ Each of the symbols independently represents a group having an ethylenically unsaturated bond, L represents a single bond or a divalent linking group that does not contain an imide bond, and * represents a bonding site with another structure.

[0127] In formula (Y-1), R １ and R ２ Each of these is preferably an independent group represented by the following formula (R1-1). In formula (R1-1), L Ｒ１ represents an n+1 valent linking group, R Ｒ１ Each of these independently represents an aromatic group, maleimide group, (meth)acryloxy group, or (meth)acrylamide group directly bonded to a vinyl group, n represents an integer from 1 to 10, and * represents A in formula (A-2). １ Or A ２ This represents the bonding site with R.Ｒ１ Each of these groups is preferably an aromatic group or a maleimide group directly bonded to a vinyl group, and more preferably a vinylphenyl group. Ｒ１ is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ It is preferably a group represented by bonding with at least one group selected from the group consisting of -, a hydrocarbon group, * １ -C(=O)-L Ｒ２ - * ２ Or, * １ -C(=O)NR Ｎ -L Ｒ２ - * ２ It is more preferable that the group is represented by the above L Ｒ１ The hydrocarbon group in is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. Ｒ２ R represents a hydrocarbon group, preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms. Ｎ Hydrogen atoms or hydrocarbon groups are preferred, hydrogen atoms or alkyl groups are more preferred, hydrogen atoms or methyl groups are even more preferred, and hydrogen atoms are particularly preferred. * １ is equivalent to * in equation (R1-1), and * ２ R in equation (R1-1) Ｒ１ This represents the bonding site with R. Ｒ１ If L is a vinylphenyl group, Ｒ１ It is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group. Ｒ１ If it is a maleimide group, L Ｒ１ is an alkylene group having 1 to 4 carbon atoms or * １ -C(=O)-L Ｒ２ - * ２ It is preferable that the group is represented by R. Ｒ１ If L is a (meth)acryloxy group or a (meth)acrylamide group, Ｒ１ teeth* １ -C(=O)NR Ｎ -LＲ２ - * ２ It is preferable that the base is represented by . n is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0128] In equation (Y-1), L is a single bond, -C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -S (=O) ２ - or 9,9-fluoroorangeyl group is preferred. Also, L is a single bond, -C(CH ３ ) ２ -, or -C(CF ３ ) ２ -This embodiment is also one of the preferred embodiments of the present invention.

[0129] In equation (Y-1), * represents Y in equation (1-2). １ It is preferable that this is the bonding site with the nitrogen atom to which it is bonded.

[0130] It is also preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0131] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0132] To improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-capturing agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0133] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. The upper limit of the above imidization rate is not particularly limited and may be 100% or less.

[0134] Polyimide is a material in which all repeating units are R １３１ and R １３２ The combination of R may include the repeating unit represented by the above formula (4), which is the same.１３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of elements. In addition to the repeating units represented by formula (4) above, the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

[0135] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0136] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimide as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the above multiple types of polyimide are treated as a single resin are, respectively, within the above range. [Polybenzoxazole precursors] Examples of polybenzoxazole precursors include the compounds described in paragraphs 0073 to 0095 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0137] [Polybenzoxazoles] Examples of polybenzoxazoles include the compounds described in paragraphs 0101-0108 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0138] [Polyamide-imide precursors] Examples of polyamide-imide precursors include the compounds described in paragraphs 0104-0119 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0139] [Polyamideimides] Examples of polyamideimides include the compounds described in paragraphs 0125-0138 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0140] [Method for producing polyimide precursors, etc.] Polyimide precursors, etc., are produced, for example, by the method described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0141] [Content] The content of the specific resin in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin in the resin composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. Furthermore, when the content of the specific resin in the resin composition is 100 parts by mass, the content of the polymerizable compound described later is preferably 1 to 15 parts by mass, more preferably 2 to 12 parts by mass, and even more preferably 3 to 10 parts by mass. The resin composition may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0142] The resin composition may also preferably contain at least two types of resins. Specifically, the resin composition may contain a total of two or more types of specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition contains two or more specific resins, for example, a polyimide precursor with a structure derived from dianhydride (R in formula (2) above) １１５ Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0143] <Other Resins> The resin composition may include the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, etc. 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 be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable compound with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10⁻⁶) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0144] If the resin composition contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solids content of the resin composition. If the resin composition contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solids content of the resin composition. As a preferred embodiment of the resin composition, the content of other resins can also be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solids content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0145] <Polymerizable Compounds> The resin composition preferably contains polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0146] [Radical Crosslinking Agent] The resin composition preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0147] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 is even more preferred. From the viewpoint of the film strength of the resulting pattern (cured product), the resin composition may also preferably contain a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0148] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0149] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0150] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0151] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0152] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0153] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0154] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0155] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0156] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0157] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0158] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-methyl-1,5-pentanediol diacrylate. Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0159] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0160] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0161] [Other Crosslinking Agents] The resin composition may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon photosensitivity with the photoacid generator or photobase generator described above, and more preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from the photoacid generator or photobase generator in the exposure process. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0162] [Polymerization Initiator] The resin composition preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator. Alternatively, the photopolymerization initiator may be a compound that generates polymerization initiator species upon heat. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible regions is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0163] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0164] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0165] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0166] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0167] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0168] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0169] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0170] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0171] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0172] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0173]

[0174] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0175] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0176] In addition, compounds described in paragraphs 0113 to 0117 of Japanese Patent Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated into the present specification.

[0177] If the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0178] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michla's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0179] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0180] [Chain Transfer Agents] The resin composition may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0181] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0182] If the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0183] [Thermal Polymerization Initiator] The resin composition may also preferably contain a thermal polymerization initiator. Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy to initiate or accelerate the polymerization reaction of polymerizable compounds. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and polymerizable compound can be advanced, thereby further improving solvent resistance.

[0184] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0185] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of thermal polymerization initiator or two or more types. If two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0186] <Base Generator> The resin composition may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, if the resin composition contains a polyimide precursor, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs 0249-0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0187] Examples of base-generating agents include, but are not limited to, the following compounds.

[0188]

[0189] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0190] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0191] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0192] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0193] Furthermore, as a base-generating agent, it is preferable that the amino group is protected by a t-butoxycarbonyl group, from the viewpoint of storage stability and base generation by deprotection during curing.

[0194] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol Luamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) Examples include, but are not limited to, ethers, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a t-butoxycarbonyl group.

[0195] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0196] <Solvent> The resin composition preferably contains a solvent. Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0197] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-A Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0198] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0199] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0200] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0201] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0202] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0203] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0204] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0205] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0206] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content can be determined by considering the solubility of specific resins and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0207] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0208] <Metal Adhesion Enhancers> From the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc., the resin composition preferably contains a metal adhesion enhancer. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0209] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0210]

[0211] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercially available products can be used as such oligomer-type compounds, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0212] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0213] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0214] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0215] <Migration Inhibitor> The resin composition preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0216] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0217] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0218] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0219] Specific examples of migration inhibitors include the following compounds.

[0220]

[0221] If the resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0222] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0223] <Polymerization Inhibitors> The resin composition preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0224] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference.

[0225] If the resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0226] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0227] <Light Absorbers> The resin composition may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Publication No. 2019-206689. These contents are incorporated herein by reference.

[0228] The content of the light absorber relative to the total solid content of the resin composition is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0229] [Surfactants] The resin composition preferably contains a surfactant. Various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0230] By incorporating a surfactant into the resin composition, the liquid properties (especially fluidity) of the composition are improved, leading to improved uniformity of coating thickness and reduced liquid consumption, as well as increased conformability of the composition to uneven surfaces. Specifically, when forming a film using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution decreases, improving wettability to the surface and enhancing coatability. As a result, air bubbles are less likely to be incorporated into uneven areas, and a more uniform film with less thickness variation can be formed more effectively.

[0231] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0232] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition. This will be incorporated into the specification.

[0233] <Other Additives> The resin composition may optionally contain various additives, such as higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention can be obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the resin composition.

[0234] <Characteristics of the Resin Composition> The viscosity of the resin composition can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, an excellent coating film can be obtained on the coated surface.

[0235] <Restrictions on the substances contained in the resin composition> The water content of the resin composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0236] From the viewpoint of insulating properties, the metal content of the resin composition is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0237] Furthermore, methods for reducing metal impurities unintentionally included in resin compositions include selecting raw materials with low metal content as components of the resin composition, filtering the raw materials of the resin composition, and performing distillation under conditions that suppress contamination as much as possible by lining the apparatus with polytetrafluoroethylene or the like.

[0238] When considering the application of the resin composition as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the halogen atoms present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chloride ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0239] Conventional containers can be used as containers for the resin composition. To suppress the incorporation of impurities into the raw materials and resin composition, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0240] <Preparation of Resin Composition> The resin composition can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0241] To remove foreign matter such as dust and fine particles from the resin composition, filtration using a filter is preferable. As a filter, for example, the filter described in paragraph 0287 of International Publication No. 2023 / 190064 can be used. This description is incorporated herein by reference.

[0242] (Jointed Body) The jointed body of the present invention is a jointed body obtained by the method for manufacturing the jointed body of the present invention. The jointed body of the present invention can be suitably used in applications such as the devices of the present invention described later.

[0243] (Device and Method for Manufacturing the Same) The device according to the present invention comprises the bonded structure of the present invention. The method for manufacturing the device according to the present invention includes the method for manufacturing the bonded structure of the present invention. The device according to the present invention includes semiconductor devices, electronic devices, etc., and is preferably a semiconductor device or an electronic device. Examples of devices include those described in "Illustrated Guide to All About Cutting-Edge Semiconductor Packaging Technology" edited by the Semiconductor New Technology Research Group, Kogyo Chosakai, pp. 8-19, 110-114, 160-165, and "Illustrated Guide to All About Surface Treatment Technology" edited by the Surface Optics Research Institute, Kanto Gakuin University, Kogyo Chosakai, pp. 32-41, 56-59. Specifically, examples include using the above-mentioned organic insulating portion as an adhesive film to replace the underfill between chips, and using the above-mentioned organic insulating portion as a die bonding film to fix the chips. In addition, the method for manufacturing the bonded structure of the present invention can be applied to a wide range of applications, such as mounting LED (light emitting diode) elements, mounting optical elements for flat panel displays, and mounting power semiconductor packages. Furthermore, for example, the method for manufacturing a bonded structure according to the present invention can be suitably used for three-dimensional mounting of semiconductor elements provided with through-silicon vias (TSVs). Figure 4 is a schematic cross-sectional view showing a three-dimensional mounting device. In this embodiment, a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are stacked is arranged on a wiring substrate 120. The plurality of semiconductor elements 101a to 101d are all made of semiconductor wafers such as silicon substrates. The laminate 101 has a structure in which a semiconductor element 101a without through-silicon vias and semiconductor elements 101b to 101d having through-silicon vias 102b to 102d are connected by flip-chip connections. The connection pads on the semiconductor element side having through-silicon vias are connected by metal bumps 103a, 103b, and 103c such as solder bumps. A resin layer 110 is formed in the gaps between each of the semiconductor elements 101a to 101d. The method for manufacturing a bonded structure according to the present invention can be used as the method for manufacturing this laminate. In other words, for example, at least one (preferably all) of the resin layers 110 can be the organic insulating portion in the method for manufacturing the bonded body of the present invention described above.In that case, solder bumps are preferably omitted. A surface electrode 120a is provided on one side of the wiring board 120. An insulating layer 115 with a rewiring layer 105 formed on it is arranged between the wiring board 120 and the laminate (substrate / substrate laminate) 101. One end of the rewiring layer 105 is connected to an electrode pad formed on the rewiring layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. A resin layer 110a is formed between the insulating layer 115 and the laminate 101. The manufacturing method for the joint of the present invention can also be used to join this insulating layer 115 and the laminate 101. That is, for example, the resin layer 110a can be the organic insulating part described above. A resin layer 110b is formed between the insulating layer 115 and the wiring board 120. The manufacturing method of the joint of the present invention can also be used to join the insulating layer 115 and the wiring board 120. That is, for example, the resin layer 110b can be the organic insulating part described above.

[0244] (Resin Composition) The resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide precursors, polyimide, polybenzoxazole precursors, and polybenzoxazole, and is a resin composition used in the organic insulating part formation step in the method for producing the bonded body of the present invention. Preferred embodiments of the resin composition of the present invention are the same as preferred embodiments of the resin composition used in the method for producing the bonded body of the present invention described above.

[0245] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, 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. Unless otherwise specified, "parts" and "%" are based on mass.

[0246] <Synthesis of Polymers> [Synthesis Example P-1: Synthesis of Resin P-1] 15.0 g (48.4 mmol) of 4,4'-oxydiphthalic anhydride, 4.74 g (16.1 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride, 12.0 g (92.3 mmol) of 2-hydroxyethyl methacrylate, 4.67 g (39.5 mmol) of 2-isobutoxyethanol, 0.05 g of hydroquinone, 22.7 g of pyridine (287 mmol), and 75 g of digrime (diethylene glycol dimethyl ether) are mixed. The mixture is stirred at 60°C for 4 hours to produce a mixture of 2-hydroxyethyl methacrylate and 2-isobutoxyethanol diesters of 4,4'-oxydiphthalic anhydride and 3,3',4,4'-biphenyltetracarboxylic anhydride. Next, the reaction mixture was cooled to -10°C, and while maintaining the temperature at -10±4°C, 16.14 g (134.1 mmol) of SOCl was added. ２After adding over 60 minutes, the reaction mixture is stirred at room temperature for 2 hours. Next, a solution of 12.06 g (56.8 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -5 to 0°C. Then, the reaction mixture is reacted at 15°C for 1 hour, after which 11.9 g of ethanol is added and the mixture is stirred at room temperature for 2 hours. After adding 0.05 g of hydroquinone, the reaction mixture is added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor is obtained by filtration, and the obtained polyimide precursor is dried under reduced pressure at 45°C for 1 day to obtain the crude polyimide precursor (P-1). The obtained crude is then dissolved in 270 g of tetrahydrofuran. The dissolution is added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor is obtained by filtration, and the obtained polyimide precursor is dried under reduced pressure at 45°C for 1 day to obtain polyimide precursor (P-1). The weight-average molecular weight of this polyimide precursor (P-1) is 23,000. ¹H-NMR confirms that the obtained polyimide precursor (P-1) is presumed to contain repeating units represented by the following formula (P-1). ¹H-NMR also confirms that the imidization rate of the polyimide precursor is 0% and the HEMA introduction rate is 70%.

[0247] [Synthesis Examples P-2 to P-4: Synthesis of Resins P-2 to P-4] These resins were synthesized in the same manner as the synthesis of resin P-1 described above, except that the acid anhydride, diamine, and alcohol used were changed as shown in the table below.

[0248]

[0249] Details of the abbreviations in the table are as follows:

[0250] [Synthesis Example P-5: Synthesis of Resin P-5] 208.7 g (401 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 6.55 g (21.1 mmol) of 4,4'-oxydiphthalic anhydride, and 345 mL of N-methylpyrrolidone (NMP) were mixed in a 3 L flask. To this, a solution of 25.0 g (116 mmol) of 3,3'-dihydroxybenzidine, 54.0 g (270 mmol) of 4,4'-diaminodiphenyl ether, and 8.19 g (75.0 mmol) of 4-aminophenol, pre-dissolved in 970 g of NMP, was added dropwise. After the dropwise addition was complete, 144 ml of toluene was added and the mixture was stirred at 180°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature. Then, 5.92 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 161 g (1055 mmol) of p-chloromethylstyrene, 175 g (1266 mmol) of potassium carbonate, 21.0 g (127 mmol) of potassium iodide, and 438 g of NMP were added, and the mixture was stirred at 90°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, diluted with 3500 ml of THF, and filtered by suction filtration. The filtrate was added dropwise to 8800 mL of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain resin (P-1) as a powder. The weight-average molecular weight of the obtained resin (P-1) was 24,600, and the number-average molecular weight was 9,900. Resin (P-1) is a resin having repeating units represented by the following formula (P-1). The structure of the repeating unit is: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0251] [Synthesis Example P-6: Synthesis of Resin P-6] In a drying reactor equipped with a stirrer, condenser, and flat-bottom joint with an internal thermometer, 10.65 g (50 mmol) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride was dissolved in 85.8 g of N-methylpyrrolidone (NMP) while removing water. Next, 9.74 g (48 mmol) of terephthalic acid chloride dissolved in 55.0 g of NMP was added dropwise over 1 hour, and the mixture was stirred at 25°C for a constant time. By increasing the constant time, the molar amount of benzoxazole structure in the polybenzoxazole precursor can be increased, and by shortening the time, the molar amount of benzoxazole structure in the polybenzoxazole precursor can be decreased. For example, by setting the time to 15 minutes, the molar amount of benzoxazole structure can be set to 0.373 mmol / g. After stirring, the mixture was precipitated in 2 liters of water / methanol = 75 / 25 (volume ratio) and stirred at 2,000 rpm for 30 minutes. The precipitated polybenzoxazole precursor resin was removed by filtration and washed with 1.5 liters of water. The resulting resin was dried under reduced pressure at 40°C for 1 day to obtain P-6.

[0252] [Synthesis Example P-7: Synthesis of Resin P-7] 29.08 g of trimellitic anhydride was placed in a separable flask, 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and the mixture was stirred at room temperature. While stirring, 24.66 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and left at room temperature for 16 hours. Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for a certain period of time, 7.17 g of ethyl alcohol was added and the mixture was stirred for 1 hour, followed by the addition of 136.83 g of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The obtained reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain powdered polymer (polyamide-imide precursor) P-7.

[0253] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed to obtain each resin composition. Similarly, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition. Specifically, the content (amount blended) of each component listed in the table other than the solvent was the amount (parts by mass) indicated in the "parts by mass" column of each column in the table. The solvent content (amount blended) was adjusted so that the solid content concentration of the composition was equal to the value (mass%) of "solid content concentration (mass%)" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent was the ratio indicated in the "ratio" column in the table. The obtained resin compositions and comparative compositions were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. In the table, "-" indicates that the composition does not contain the corresponding component. The content of polymerizable compounds when the content of a specific resin is 100 parts by mass is indicated in the "monomer / binder ratio" column.

[0254]

[0255]

[0256]

[0257] [Resin] ・P-1 to P-7: Resins P-1 to P-7 synthesized as described above

[0258] [Polymerizable compounds] ・A-1: Dipentaerythritol hexaacrylate ・A-2: SR-209 (manufactured by Sartomer Co., Ltd.) ・A-3: Light acrylate 3EG-A (manufactured by Kyoeisha Chemical Co., Ltd.)

[0259] [Photopolymerization Initiators] ・B-1: SpeedCure PDO (Sartomer Co., Ltd.) ・B-2: Irgacure OXE02 (BASF Corporation) ・B-3: Irgacure OXE01 (BASF Corporation)

[0260] [Thermal base generator] ・C-1: Compound with the following structure

[0261] [Polymerization inhibitors] ・D-1: Compounds with the following structure

[0262] [Silane coupling agents] • E-1: Compound with the following structure • E-2: Compound with the following structure

[0263] [Migration Inhibitors] • F-1: Compound with the following structure • F-2: 5-aminotetrazole

[0264] [Additives] ・G-1: N-phenyldiethanolamine ・G-2: BYK-333 (manufactured by BYK Chemie) ・H-1: Compound with the following structure

[0265] [Solvents] GBL: γ-butyrolactone, DMSO: dimethyl sulfoxide, Cyclopentanone: cyclopentanone

[0266] <Fabrication of Substrates A and B> Pillar substrates with the following size and metal type were fabricated by plating. Pitch: 20 μm, Pillar diameter: 20 μm, Pillar height: 6 μm, Silicon wafer, Pillar is formed in this order. Details of the pillars are described in the "Electrode A" and "Electrode B" columns of the table, respectively. For example, if the "Electrode A" column of the table is listed as "Cu / SnAg" and "2 μm / 4 μm", it refers to Substrate A, which is formed in the order of Silicon wafer, Cu electrode (height 2 μm), and SnAg electrode (height 4 μm). For example, if the "Electrode B" column of the table is listed as "Cu / SnAg" and "2 μm / 4 μm", it refers to Substrate B, which is formed in the order of Silicon wafer, Cu electrode (height 2 μm), and SnAg electrode (height 4 μm).

[0267] Details of the fabricated pillar substrate are described below. Figure 5 is a schematic cross-sectional view of substrate A, which is formed in the order of silicon wafer, Cu electrode (height 2 μm), and SnAg electrode (height 4 μm). In Figure 5, 10 represents the substrate and 12 represents the electrode. The electrode 12 is formed from a pillar (conduit) 14 made of SnAg and a pillar (electrode part) 16 made of Cu. In Figure 5, the arithmetic mean of the diameter d of each pillar is the pillar diameter, which is 20 μm in substrate A. In Figure 5, the arithmetic mean of the spacing p between pillars in each pillar is the pitch, which is 20 μm in substrate A. In Figure 5, the arithmetic mean of the height h1 of the conduit in each pillar is the tin pillar height, which is 4 μm in substrate A. In Figure 5, the arithmetic mean of the height h2 of the electrode in each pillar is the copper pillar height, which is 2 μm in substrate A.

[0268] <Preparation of Substrates / Substrate Laminates (Bonds)> [Preparation of Substrate A Having an Organic Insulating Part, Evaluation of Dissolution Rate] In each example and comparative example, the composition prepared in each example or comparative example was applied to the above-mentioned Substrate A, baked at 100°C for 5 minutes to obtain a resin composition film with the thickness indicated in the "Film Thickness (μm)" column of the table. Subsequently, development treatment was carried out using a developing machine equipped with the organic solvent and spray nozzle indicated in the "Organic Solvent" column of the table to reduce the film thickness to 6 μm (film thickness reduction treatment). From the time until the above reduction was completed, the dissolution rate of the resin composition film in the organic solvent was calculated and indicated in the "Dissolution Rate nm / sec" column of the table. Subsequently, the resin composition film was heated under the temperature and time conditions indicated in the "Cure Temperature (°C)" and "Cure Time (min)" columns of the table to obtain a cured product. The surface of the above-mentioned hardened material was polished using CMP (Chemical Mechanical Polishing) manufactured by Fujikoshi Machinery Industries, Ltd., so that the polished film thickness was the amount indicated in the "CMP Polished Film Thickness (nm)" column of the table. In the example where "alumina" was indicated, an alumina slurry (Polifine A100-Type MX manufactured by Kemet Japan) was used, and in the example where "silica" was indicated, a silica slurry was used to form the organic insulating layer. The time from the start of the above film thickness reduction treatment to the formation of the organic insulating layer is indicated in the "Process Time (sec)" column. The process time was also evaluated according to the following evaluation criteria, and the evaluation results are indicated in the "Process Time (sec)" column of the table. -Evaluation Criteria- A: The process time was 100 seconds or less. B: The process time was more than 100 seconds but 300 seconds or less. C: The process time was more than 300 seconds but 500 seconds or less. D: The process time was more than 500 seconds.

[0269] [Preparation of base material B] Using the same composition as for the preparation of base material A having the organic insulating portion described above, and the same method as described above for base material B, base material B having the organic insulating portion was obtained.

[0270] [Evaluation of Bonding and Voids] Substrates A and B were then cut into 5 mm squares using a dicing machine to produce chips. These chips were then bonded using a flip-chip bonder manufactured by Toray Engineering Co., Ltd., under the temperature, time, and pressure conditions listed in the "Bonding Conditions" column of the table to obtain bonded bodies. Ten bonded bodies were produced in each example by performing the same bonding procedure. Subsequently, void evaluation was performed by cross-sectional SEM observation of the wiring section. The evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in the "Large Pitch Voids" column of the table. -Evaluation Criteria- A: 0 chips with voids B: 1 chip with voids C: 2 or more chips with voids

[0271] [Biased HAST (Highly Accelerated Stress Test) Test] A biased HAST test was performed in each example and each comparative example. The biased HAST test was performed using a simple test vehicle 100 as shown in Figure 6. Figure 6 is a schematic cross-sectional view of the test vehicle used in the biased HAST test. The test vehicle 100 has SiO on a Si wafer (silicon wafer) 102. ２ Layer 104, a patterned Ti layer 106, and patterned 2 μm L / S (line and space) comb-shaped copper wiring 108 are stacked in this order, and the wiring is covered with cured products 110 of each composition. In Figure 1, d3 and d4 are 2 μm. Specifically, SiO contained in the test vehicle ２ Coating films of each resin composition were formed on the wafer and Cu wiring. Then, a cured product 110 was formed using the same method as described in "Preparation of Substrate A" above. A bias HAST test was performed using each test vehicle. The bias HAST test was conducted using a Hirayama oven at 130°C / 85% RH (relative humidity) / 96h (96 hours). The voltage applied during the HAST test was 15V, and the test was determined by whether or not there was a short circuit in the wiring during the test. The electrical resistance value was 10 ５A short circuit was determined when the resistance fell below Ω. The evaluation results are recorded in the "Reliability" column of the table. -Evaluation Criteria- A: No short circuit was detected in the wiring at 96 hours. B: A short circuit was detected in the wiring between 61 hours and 96 hours. C: A short circuit was detected in the wiring between 31 hours and 61 hours. D: A short circuit was detected in less than 31 hours.

[0272] From the above results, it can be seen that the method for manufacturing a bonded body according to the present invention can shorten the time required for the polishing process in the manufacturing of the bonded body and suppress the generation of voids. The method for manufacturing a bonded body according to Comparative Example 1 does not include a removal step. In such a manufacturing method, it can be seen that the time required for the polishing process is long and voids are generated. Furthermore, in the method for manufacturing a bonded body according to Comparative Example 2, the thickness of the resin composition film is about 1.3 times the height of electrode A (8 μm / 6 μm). In such an embodiment, it can be seen that voids are likely to be generated.

[0273] 1 Substrate A (Underlayment, Daughter Chip) 1x Silicon wafer 1y Substrate with Organic Insulation 1z Laminate 2 Substrate B (Mother Chip) 2a Surface of the second organic insulation on Substrate B 2x Silicon wafer 2y Through-hole electrode 31 Electrode (metal part) 31a Tip of electrode 32 Electrode (metal part) 4 Resin composition film 4a Surface of organic insulation (before planarization) 4b Surface of organic insulation (after planarization) 41 Organic insulation 42 Second organic insulation 51 Organic insulation 8 Electronic circuit region 10 Substrate 12 Electrode A 14 Conductor 16 Electrode part 81 Electronic circuit 90 Semiconductor device 100 Bonded body 101a-101d Semiconductor element 101 Bonded body 102b-102d Through-hole electrode 103a-103e Metal bump 105 Redistribution layer 110, 110a, 110b Resin layer 115 Insulating layer 120 Wiring board 120a Surface electrode 200 Semiconductor device 300 Test vehicle 302 Si wafer 304 SiO ２Layer 306 Ti layer 308 Cu wiring 310 Cured material d Pillar diameter p Pillar spacing h Pillar height h1 Conduction path height h2 Electrode height

Claims

1. A method for manufacturing a bonded body, comprising the steps of: preparing a base material A having a surface equipped with an electrode A; forming an organic insulating portion on the surface of the base material A equipped with the electrode A; preparing a base material B having a surface equipped with an electrode B; and joining the surface of the base material A equipped with the organic insulating portion and the surface of the base material B equipped with the electrode B, wherein the organic insulating portion forming step comprises the steps of: applying a resin composition to the surface of the base material A equipped with the electrode A to form a resin composition film having a film thickness of 1.5 times or more the height of the electrode A; and removing the resin composition film with an organic solvent to reduce its film thickness.

2. The method for producing a bond according to claim 1, wherein the resin composition comprises at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.

3. The method for manufacturing a bonded body according to claim 1 or 2, wherein the electrode A contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti.

4. The method for manufacturing a bonded body according to claim 1 or 2, wherein the electrode B contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti.

5. The method for producing a bonded body according to claim 1 or 2, wherein in the removal step, the dissolution rate of the resin composition film in the organic solvent is 10 nm / sec or more.

6. The method for producing a bonded body according to claim 1 or 2, wherein in the removal step, the dissolution rate of the resin composition film in the organic solvent is less than 200 nm / sec.

7. The method for producing a bonded body according to claim 1 or 2, wherein the dissolution rate of the resin composition film in cyclopentanone is 10 nm / sec or more and less than 200 nm / sec.

8. The method for producing a bonded body according to claim 1 or 2, wherein the content of the polymerizable compound in the resin composition is 1 to 15% by mass, when the content of the resin in the resin composition is 100% by mass.

9. A method for producing a bond according to claim 1 or 2, wherein the resin comprises a polyimide precursor containing repeating units represented by the following formula (1-1). In formula (1-1), X is a tetravalent organic group, Y is a divalent organic group, and R １ and R ２ Each is independently a hydrogen atom or an organic group, R １ and R ２ At least one of these can be expressed by the following formula (III). In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group. ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or polyalkylene oxy group, and * represents a bond site with an oxygen atom.

10. The method for producing an assembled body according to claim 9, wherein the polyimide precursor is a repeating unit represented by formula (1-1), and X in formula (1-1) comprises a repeating unit B represented by the following formula (a) or (b). In formula (a) or formula (b), * represents the bonding site with the carbonyl group in formula (1-1).

11. The method for producing the bonded body according to claim 1 or 2, wherein the resin contains a polyimide having a repeating unit represented by the following formula (1-2). In formula (1-2), X １ is a tetravalent organic group, and Y １ is a divalent organic group having a group containing an ethylenic unsaturated bond.

12. A joint manufactured by the method for manufacturing a joint described in claim 1 or 2.

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

14. A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole, used in the organic insulating part forming step in the method for producing a joint according to claim 1 or 2.

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