Joined body, method for producing joined body, photosensitive resin composition, and semiconductor device

Abstract

Provided is a joined body obtained by joining a first member that has a first base material, a first insulation pattern which is disposed on the first base material, and a first conductive pattern which exists in pattern spaces of the first insulation pattern, and a second member that has a second base material, a second insulation pattern which is disposed on the second base material, and a second conductive pattern which exists in pattern spaces of the second insulation pattern, wherein in the joined body, the angle formed by a bottom surface of the first conductive pattern and a side surface of the first conductive pattern is greater than 90° but not more than 110°. Also provided are a method for producing the joined body, a photosensitive resin composition used in the method for producing the joined body, and a semiconductor device comprising the joined body.

Description

Joint, method for manufacturing joint, photosensitive resin composition, and semiconductor device

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

[0002] Electronic devices such as mobile phones and tablet devices are becoming increasingly smaller while their functions are becoming more diverse. To meet these needs, electronic circuits incorporated into electronic devices require further miniaturization, higher integration, and higher-density packaging, necessitating advances in multilayer wiring technology. Conventional methods for manufacturing components with multilayer wiring technology include the semi-additive process (SAP) and the damascene process. The SAP process involves forming a resist pattern in advance in non-circuit areas, plating the circuit areas, and then removing the resist pattern to form pillar electrodes. The spaces between the pillar electrodes are then filled with an insulating material, which is then polished to expose the pillar electrodes. The damascene process involves forming pillar-shaped holes in an insulating film and filling them with a metal such as copper. The damascene process has the advantage of being easy to use as a wiring material, even for metals that are difficult to dry etch, such as copper.

[0003] A known damascene method is the single damascene method, which is a method for forming a hole pattern by, for example, burying copper wiring in an insulating film in which via holes have been formed and polishing the resulting insulating film.

[0004] For example, Patent Document 1 discloses a method for manufacturing a semiconductor device, the method comprising: a step of preparing a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body; a step of preparing a second semiconductor substrate having a second substrate body, a second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body; a step of singulating the second semiconductor substrate to obtain a plurality of semiconductor chips, each of which has an insulating film portion corresponding to the second organic insulating film and at least one of the second electrodes; and a step of heating and pressurizing the first semiconductor substrate and the semiconductor chip to bond the first organic insulating film and the insulating film portion together and to bond the first electrode and the second electrode together, wherein before heating the first semiconductor substrate and the semiconductor chip, at least one of a first protrusion amount by which the first electrode protrudes from the surface of the first organic insulating film and a second protrusion amount by which the second electrode protrudes from the surface of the second organic insulating film or the insulating film portion is a protrusion amount within 130% of a protrusion amount ΔL calculated by a specific method.

[0005] International Publication No. 2023 / 228321

[0006] When a member on which a conductive pattern (pillar) is formed is to be joined to another member, it is required that the peel resistance after joining be large.

[0007] An object of the present invention is to provide a bonded structure having a high peel resistance, a method for manufacturing the bonded structure, a photosensitive resin composition used in the method for manufacturing the bonded structure, and a semiconductor device including the bonded structure.

[0008] Specific examples of the present invention are described below: <1> A bonded structure obtained by bonding a first member having a first base material, a first insulating pattern arranged on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern arranged on the second base material, and a second conductive pattern present between the second insulating patterns, wherein an angle formed between a bottom surface of the first conductive pattern and a side surface of the first conductive pattern in the bonded structure is greater than 90° and not greater than 110°. <2> A bonded structure formed by bonding a first substrate, a first member having a first insulating pattern arranged on the first substrate, and a first conductive pattern present between the first insulating patterns, and a second member having a second substrate, a second insulating pattern arranged on the second substrate, and a second conductive pattern present between the second insulating patterns, wherein an angle formed between a bottom surface of the first conductive pattern and a side surface of the first conductive pattern in the first member before the bonding is greater than 90° and not greater than 110°. <3> The bonded structure according to <1> or <2>, wherein a difference between a maximum value and a minimum value of a distance from a surface of the first substrate of the first member to a surface of the first conductive pattern on a side opposite the first substrate in a direction perpendicular to the surface of the first substrate of the first member before the bonding is 500 nm or less. <4> The bonded body according to any one of <1> to <3>, wherein the first conductive pattern in the first member before the bonding is a pillar pattern and has a diameter of 0.1 μm or more and 10 μm or less. <5> The bonded body according to any one of <1> to <4>, wherein the first conductive pattern in the first member before the bonding contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti. <6> The bonded body according to any one of <1> to <5>, wherein a surface of the first conductive pattern in the first member before the bonding contains at least Sn.<7> The bonded structure according to any one of <1> to <5>, wherein a surface of the first conductive pattern in the first member before the bonding contains at least Cu. <8> The bonded structure according to any one of <1> to <7>, wherein the indentation modulus of the first insulating pattern in the first member before the bonding is 6.0 GPa or less. <9> The bonded structure according to any one of <1> to <8>, wherein the first insulating pattern in the first member before the bonding contains polyimide. <10> The bonded structure according to <9>, wherein the cyclization rate of the polyimide is 70% or more. <11> The bonded structure according to any one of <1> to <10>, wherein the first insulating pattern in the first member before the bonding contains an ionic compound. <12> The bonded body according to any one of <1> to <11>, wherein the second conductive pattern in the second member before the bonding is a pillar pattern or a pad pattern, and the diameter or side length of the second conductive pattern is 0.1 μm or more and 10 μm or less. <13> The bonded body according to any one of <1> to <12>, wherein the second conductive pattern in the second member before the bonding contains at least one of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti. <14> The bonded body according to any one of <1> to <13>, wherein a surface of the second conductive pattern in the second member before the bonding contains at least Sn. <15> The bonded body according to any one of <1> to <13>, wherein a surface of the second conductive pattern in the second member before the bonding contains at least Cu. <16> The bonded body according to any one of <1> to <15>, wherein the second insulating pattern in the second member before bonding has an indentation elastic modulus of 6.0 GPa or less. <17> The bonded body according to any one of <1> to <16>, wherein the second insulating pattern in the second member before bonding contains a polyimide. <18> The bonded body according to <17>, wherein the cyclization rate of the polyimide is 70% or more. <19> The bonded body according to any one of <1> to <18>, wherein the second insulating pattern in the second member before bonding contains an ionic compound.<20> The bonded body according to any one of <1> to <19>, wherein the second insulating pattern in the second member before the bonding includes an inorganic insulating film. <21> The second insulating pattern in the second member before the bonding is made of SiN or SiO. ２<22> The bonded structure according to any one of <1> to <21>, wherein at least one of the first base material and the second base material includes a redistribution layer. <23> A method for manufacturing a bonded body that bonds a first member having a first base material, a first insulating pattern arranged on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern arranged on the second base material, and a second conductive pattern present between the second insulating patterns, the method comprising: a conductive layer forming step of forming a conductive layer in regions between the first insulating patterns of the first base material on which the first insulating pattern is formed and on the first insulating pattern to obtain a member A; a polishing step of polishing the member A to obtain a first member having the first conductive pattern and the first insulating pattern exposed on a surface thereof; and a bonding step of bonding the first member and a second member to obtain a member, wherein an angle formed between a bottom surface of the conductive pattern of at least the first member and a side surface of the conductive pattern is greater than 90° and not greater than 110°. <24> The method for producing a bonded body according to <23>, further comprising, before the conductive layer forming step, a film forming step including applying a first insulating pattern forming composition to the first base material to form a film, wherein the first insulating pattern forming composition contains at least one compound selected from the group consisting of a photoradical polymerization initiator and a photoacid generator. <25> The method for producing a bonded body according to <24>, further comprising, after the film forming step, a drying step of drying the film, an exposure step of exposing the dried film to light, and a development step of developing the exposed film with a developer, wherein the first insulating pattern forming composition is applied to a silicon wafer and heated at 100°C for 180 seconds, and then the i-line transmittance of the film is 100 mJ / cm. ２and heating at 110°C for 3 minutes, the swelling ratio of the film in the developer is 15% by volume or less. <27> The method for producing a bonded body according to <26>, comprising, after the film-forming step, a heating step of heating the film at two or more heating temperatures. <28> The method for producing a bonded body according to any one of <23> to <27>, wherein at least one of the first base material and the second base material includes a redistribution layer. <29> A photosensitive resin composition used in forming the first insulating pattern in the production method according to any one of <23> to <27>. <30> The photosensitive resin composition according to <29>, comprising a polyimide or a polyimide precursor. <31> A semiconductor device comprising the bonded body according to any one of <1> to <22>.

[0009] According to the present invention, there are provided a bonded structure having a high peel resistance, a method for manufacturing the bonded structure, a photosensitive resin composition used in the method for manufacturing the bonded structure, and a semiconductor device including the bonded structure.

[0010] 1 is a schematic cross-sectional view showing an example of a first member of the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a case where a first conductive pattern is distorted. FIG. 1 is a schematic cross-sectional view showing an example of a bonded body of the present invention in which a first member and a second member are bonded. FIG. 1 is a process explanatory diagram showing, in cross-sectional views, a process of a method for manufacturing a first member according to one embodiment of the present invention. FIG. 1 is a process explanatory diagram showing, in cross-sectional views, another example of a process (part) of a method for manufacturing a first member according to a method for manufacturing a bonded body of the present invention. FIG. 1 is a schematic cross-sectional view of an interposer wafer used in the examples.

[0011] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the 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, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8420GPC (manufactured by Tosoh Corporation) and guard columns SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by Tosoh Corporation) connected in series in this order as columns. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, when NMP is not suitable as the eluent, for example, due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting the conjugate is described as "above" or "below," it is sufficient that another layer is 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 layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up." Alternatively, if a resin composition layer is present, 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 such up-and-down directions are defined for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from the vertically upward direction. Unless otherwise specified in this specification, the composition may contain two or more compounds corresponding to each component contained in the composition. Unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. Unless otherwise specified in this specification, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, combinations of preferred embodiments are more preferred embodiments.

[0012] (Jointed Structure) A joined structure according to a first aspect of the present invention (hereinafter also referred to as a "first joined structure") is a joined structure obtained by joining together a first member having a first base material, a first insulating pattern arranged on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern arranged on the second base material, and a second conductive pattern present between the second insulating patterns, wherein an angle formed between a bottom surface of the first conductive pattern and a side surface of the first conductive pattern in the joined structure is greater than 90° and not greater than 110°. A bonded structure according to a second aspect of the present invention (hereinafter also referred to as a "second bonded structure") is a bonded structure formed by bonding a first member having a first substrate, a first insulating pattern disposed on the first substrate, and a first conductive pattern present between the first insulating patterns, to a second member having a second substrate, a second insulating pattern disposed on the second substrate, and a second conductive pattern present between the second insulating patterns, wherein the angle formed between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the first member before bonding is greater than 90° and less than 110°. In this specification, a bonded structure corresponding to the first bonded structure or the second bonded structure is also simply referred to as a "bonded structure of the present invention." In this specification, a bonded structure refers to a state in which a first member and a second member are in contact with each other and integrated, and may further include other members. Furthermore, it is sufficient that the first member and the second member are in contact with each other in the bonded body, and it is not necessarily limited to a body that has undergone a bonding step such as the bonding step described below.

[0013] Conventionally, methods such as the SAP (Semi-Additive Process) method and the Damascene method have been used to manufacture components with wiring formed using multilayer wiring technology. The Damascene method polishes the metal on the insulating film that overflows from the via hole when filling the via hole, thereby achieving a flat structure that is difficult to achieve with the SAP method. Additionally, the Damascene method has the advantage of reducing the number of manufacturing steps compared to the SAP method, thereby reducing manufacturing costs. Here, when bonding a component formed using the SAP or Damascene method to another component, a high peel resistance after bonding is required. In a bonded structure according to a first aspect of the present invention, the angle between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the bonded structure is greater than 90° and less than 110°. In a bonded structure according to a second aspect of the present invention, the angle between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the first component before bonding is greater than 90° and less than 110°. Here, if the angle between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the first member before bonding is greater than 90° and less than 110°, the angle between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the bonded body will also be greater than 90° and less than 110°. When the angle in the bonded body exceeds 90°, stress is less likely to be applied to the lower end of the conductive pattern when the bonded body is thermally or mechanically deformed, thereby suppressing peeling of the conductive pattern and increasing the peel resistance after bonding. Furthermore, when the angle is 110° or less, it is believed that fine patterns can be formed. Furthermore, as described above, peeling of the conductive pattern is suppressed, and when the angle exceeds 90°, the total area of ​​the conductive pattern exposed at the bonding surface is increased, resulting in excellent conductivity and reliability. In addition, when polishing is performed, it is thought that by setting the angle above 90°, stress is less likely to be applied to the lower end of the conductive pattern during polishing, and peeling of the conductive pattern during polishing is also suppressed. Furthermore, when the angle above 90° is set, the total area of ​​the insulating pattern exposed on the polished surface becomes smaller compared to when the angle is 90° or less.As a result, the amount of polishing debris generated during polishing due to the insulating pattern is reduced, and the occurrence of scratches on the polished surface of the component can be suppressed. Furthermore, when a seed layer is formed, it is thought that by setting the angle to more than 90°, a uniform and dense sputtering film can be formed during the seed layer formation by sputtering, which suppresses peeling of the conductive pattern and increases the peel resistance after bonding.

[0014] Patent Document 1 neither describes nor suggests that the angle between the bottom surface of the conductive pattern and the side surface of the conductive pattern is greater than 90° and not greater than 110°. Hereinafter, the bonded structure of the present invention will be described in detail.

[0015] The first member of the present invention includes a first member having a first base material, a first insulating pattern disposed on the first base material, and a first conductive pattern present between the first insulating patterns. Details of the first member before bonding will be described below.

[0016] [First Substrate] The substrate is not particularly limited, and may be a semiconductor substrate such as silicon, silicon nitride, polysilicon, silicon oxide, or amorphous silicon; quartz, glass, an optical film, a ceramic material, a vapor deposition film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe; paper; a spin-on-glass (SOG) substrate; a thin-film transistor (TFT) array substrate; or an electrode plate for a plasma display panel (PDP). The substrate may have a surface layer such as an adhesion layer or an oxide layer formed from hexamethyldisilazane (HMDS), a sealant (epoxy molding compound: EMC), or the like. The substrate may be in wafer or panel form. In the present invention, a semiconductor substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred. The substrate may have an electronic circuit region including an electronic circuit. The electronic circuit may also have elements such as semiconductors. The electronic circuit is preferably electrically connected to the conductive pattern. The first substrate may be in the form of a wafer or a chip, but a wafer is also a preferred embodiment 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. The shape of the first substrate is not particularly limited, and examples include a polygonal flat plate, a disk, and a polyhedron. The thickness of the first substrate is preferably 0.1 to 5 mm, and more preferably 0.2 to 1 mm.

[0017] [First Insulating Pattern] The first insulating pattern preferably contains polyimide or polybenzoxazole, more preferably polyimide. The content of polyimide or polybenzoxazole (when two or more types are contained, the total content thereof) is preferably 20 to 99.5 mass%, more preferably 30 to 99 mass%, even more preferably 40 to 98 mass%, and particularly preferably 50 to 97 mass%, relative to the total mass of the first insulating pattern. The cyclization rate (imidization rate) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the cyclization rate, as long as it is 100% or less. The cyclization rate is measured by the method described below. The first insulating pattern is preferably a cured product of the photosensitive resin composition described below. Although another layer may be formed between the first insulating pattern and the substrate, it is preferable that the first insulating pattern be in contact with the substrate.

[0018] The first insulating pattern is not particularly limited, but is preferably a hole pattern. When the insulating pattern is a hole pattern, the diameter of the bottom surface of the hole pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm. When the shape of the bottom surface of the hole pattern is not circular, the diameter is calculated as the equivalent circle diameter. The equivalent circle diameter is the diameter of a circle having the same area as the area of ​​the bottom surface of the hole pattern.

[0019] The thickness of the first insulating pattern is not particularly limited, but is preferably 100 nm or more, more preferably 300 nm or more, even more preferably 500 nm or more, and even more preferably 1 μm or more. There is no particular upper limit, but it is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The thickness of the film can be measured using a known film thickness measuring device. In this specification, thickness refers to the length in the direction perpendicular to the substrate surface.

[0020] The indentation elastic modulus of the first insulating pattern is not particularly limited, but is preferably 6.0 GPa or less, more preferably 4 to 6 GPa, and even more preferably 4.5 to 5.5 GPa. The indentation elastic modulus can be measured by a nanoindentation test.

[0021] The first insulating pattern preferably contains an ionic compound. The content of the ionic compound is preferably 0.001 to 5 mass %, more preferably 0.01 to 3 mass %, and even more preferably 1 to 2 mass %, relative to the total mass of the insulating pattern. Examples of the ionic compound include a photoacid generator and a base generator, which will be described later. Details of these compounds will be described later in the description of the photosensitive resin composition.

[0022] [First Conductive Pattern] The first conductive pattern is present between the first insulating patterns. The first conductive pattern is preferably a conductive pattern that fills the areas between the first insulating patterns. "Filling" refers to filling the areas between the patterns so that no voids are formed in the areas between the patterns. Another layer, such as a seed layer, may be present in the areas between the patterns.

[0023] The first conductive pattern 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), indium (In), antimony (Sb), and titanium (Ti). It is more preferable that the first conductive pattern contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti. It is even more preferable that the first conductive pattern contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, and Al. It is particularly preferable that the first conductive pattern contains Cu or Sn. In this specification, the inclusion of at least one of metal X or an alloy containing that metal is collectively referred to as "containing metal X." The alloy may contain elements other than those listed above. For example, the copper alloy may contain silicon atoms to form a Corson alloy. Furthermore, unavoidable dissolved oxygen or organic residues of raw material compounds mixed in during precipitation may be present. The first conductive pattern may be a conductive pattern comprising a plurality of different components. Examples include a conductive pattern comprising, in this order, a titanium layer formed by sputtering, a copper layer formed by sputtering, and a copper layer formed by plating, or a conductive pattern comprising, in this order, a titanium layer formed by sputtering, a copper layer formed by sputtering, and a tin layer formed by plating. Among these, the conductive pattern is preferably a pattern made of Sn or Cu. Furthermore, it is preferable that the surface of the first conductive pattern contains at least Sn, or that the surface of the first conductive pattern contains at least Cu.

[0024] The conductive pattern is preferably a pillar pattern. A pillar pattern refers to a columnar electrode pattern, and the ratio of the height to the circle-equivalent diameter of the base (height / circle-equivalent diameter) is preferably 0.1 to 10, and more preferably 0.2 to 5. Furthermore, when the conductive pattern is a pillar pattern, the diameter of the conductive pattern is preferably 0.1 μm or more and 10 μm or less, more preferably 0.2 to 7.5 μm, and even more preferably 0.5 to 5 μm.

[0025] The first conductive pattern may be in contact with the first insulating pattern, or may further include a first seed layer or the like between the first conductive pattern and the first insulating pattern.

[0026] [First seed layer] The first member of the present invention may further include a first seed layer (a power supply layer for electrolytic copper plating). The first seed layer is preferably present between the first insulating pattern and the first conductive pattern. Examples of the first seed layer include a layer made of a metal such as titanium, chromium, nickel, or tantalum.

[0027] [Distance from the surface of the first substrate to the surface of the first conductive pattern on the side opposite the substrate] In the first member of the present invention, the difference between the maximum and minimum distances from the surface of the first substrate to the surface of the first conductive pattern on the side opposite the first substrate in a direction perpendicular to the first substrate surface of the first member is preferably 500 nm or less. The difference between the maximum and minimum values ​​is more preferably 400 nm or less, and even more preferably 300 nm or less. Figure 1 is a schematic cross-sectional view showing an example of the first member of the present invention. In Figure 1, a silicon wafer 100a is provided with SiO ２ A first insulating pattern 102 is formed on a first substrate 100 having a layer 100b made of, and a first seed layer 104 and a first conductive pattern 106 are formed in the regions between the first insulating pattern 102. Here, h1, h2, and h3 are examples of distances from the substrate surface to the surface of the first conductive pattern on the opposite side of the substrate. Of the distances from the substrate surface to the surfaces of the conductive patterns on the opposite side of the substrate, such as h1, h2, and h3, it is preferable that the difference between the minimum and maximum values ​​is 500 nm or less.

[0028] [First Pattern Angle] In the first member of the first bonded body of the present invention (i.e., the first member included in the bonded body after bonding), the angle between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern (also referred to as the "first pattern angle after bonding") is greater than 90° and less than 110°. In the first member after bonding in the second bonded body of the present invention, the first pattern angle after bonding is preferably greater than 90° and less than 110°. The first pattern angle after bonding is preferably greater than 90° and less than 105°, and more preferably greater than 90° and less than 100°. In FIG. 1 , the angle indicated as θ is an example of the first pattern angle after bonding. In the present invention, it is sufficient that at least one first pattern angle after bonding is greater than 90° and less than 110°, but it is preferable that the average value of all first pattern angles after bonding is greater than 90° and less than 110°. In another preferred embodiment of the present invention, the first pattern angle after all bonding is greater than 90° and less than 110°. Here, when there is distortion in the sidewall of the first conductive pattern, the angle formed by the bottom surface of the first conductive pattern and a straight line connecting the end point of the bottom surface of the first conductive pattern and the end point of the exposed portion of the first conductive pattern on the side opposite the substrate is defined as the first pattern angle after bonding. Figure 2 is a schematic cross-sectional view showing an example in which the first conductive pattern is distorted. Figure 2 illustrates only the first member in the bonded structure, omitting the second member. In Figure 2, the angle θ formed by the dashed line connecting the end point b of the bottom surface of the first conductive pattern and the end point a of the exposed portion of the first conductive pattern on the side opposite the substrate and the bottom surface of the first conductive pattern is the first pattern angle after bonding. The bottom surface refers to the surface of the first conductive pattern facing the first substrate. The angle of the first pattern after bonding can be adjusted by setting the composition of the photosensitive resin composition (type of resin, physical properties of the polymerizable compound) described below, exposure conditions such as the exposure amount, exposure time, and focus position in the exposure step, and the developer in the development step.

[0029] In the first member before bonding in the first bonded body of the present invention (i.e., the first member included in the bonded body before bonding), the angle between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern (also referred to as the "first pattern angle before bonding") is preferably greater than 90° and less than 110°. In the first member after bonding in the second bonded body of the present invention, the first pattern angle before bonding is greater than 90° and less than 110°. The first pattern angle before bonding is preferably greater than 90° and less than 105°, and more preferably greater than 90° and less than 100°. Here, similar to the first pattern angle after bonding, when there is distortion in the side wall of the first conductive pattern, the angle formed by the bottom surface of the first conductive pattern and a straight line connecting an end point of the bottom surface of the first conductive pattern and an end point of the exposed portion of the first conductive pattern on the side opposite the substrate is defined as the first pattern angle before bonding.

[0030] <Second Member> The second member of the present invention has a second base material, a second insulating pattern disposed on the second base material, and a second conductive pattern present between the patterns of the second insulating pattern.

[0031] [Second Substrate] As the second substrate in the second member, the same material as the first substrate in the first member described above can be used, and the preferred embodiments are also the same.

[0032] [Second insulating pattern] The second insulating pattern is made of SiO ２Preferably, the insulating film is an inorganic insulating film containing at least one of SiN and SiCN, or an organic insulating film containing polyimide or polybenzoxazole, and from the viewpoint of productivity, it is preferable that the insulating film contains an inorganic insulating film. Furthermore, from the viewpoints of productivity and adhesion, it is also a preferred embodiment of the present invention that the second insulating pattern contains polyimide. When polyimide or polybenzoxazole is used, the content of polyimide or polybenzoxazole and the cyclization rate (imidization rate) of the polyimide can be the same as those of the first insulating pattern in the first member described above, and the same preferred embodiments apply. The same also applies to other components that may be contained. Furthermore, although another layer may be formed between the second insulating pattern and the second substrate, it is preferable that the second insulating pattern be in contact with the second substrate.

[0033] The second insulating pattern is preferably a hole pattern or a land pattern. When the second insulating pattern is a hole pattern, the diameter of the bottom surface of the hole pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm. When the shape of the bottom surface of the hole pattern is not circular, the diameter is calculated as the equivalent circle diameter. The equivalent circle diameter is the diameter of a circle having the same area as the area of ​​the bottom surface of the hole pattern. When the second insulating pattern is a land pattern, the length of the side of the bottom surface of the land pattern is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 2 μm. When the shape of the bottom surface of the land pattern is not square, the length of the side is calculated as the length of the long side.

[0034] The thickness of the second insulating pattern is not particularly limited, but is preferably 100 nm or more, more preferably 300 nm or more, even more preferably 500 nm or more, and even more preferably 1 μm or more. There is no particular upper limit, but it is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be measured using a known film thickness measuring device.

[0035] The indentation elastic modulus of the second insulating pattern is not particularly limited, but is preferably 6.0 GPa or less, more preferably 4.0 to 6.0 GPa, and even more preferably 4.5 to 5.5 GPa. The indentation elastic modulus can be measured by a nanoindenter method.

[0036] [Second Conductive Pattern] The second conductive pattern provides electrical continuity to the region between the second insulating patterns. Preferably, the second conductive pattern is a second conductive pattern that fills the region between the second insulating patterns. "Filling" refers to filling the region between the patterns so as not to leave any voids between the patterns. Another layer, such as a second seed layer, may be present in the region between the patterns.

[0037] Preferred aspects of the second conductive pattern are the same as the preferred aspects of the first conductive pattern of the first member described above. Furthermore, the second conductive pattern is preferably a pillar pattern or a pad pattern. A pad pattern refers to a flat electrode pattern, and the ratio of the height to the circle-equivalent diameter of the bottom surface (height / circle-equivalent diameter) is preferably 0.001 to 5, more preferably 0.01 to 2. Preferred aspects of the pillar pattern are the same as the preferred aspects when the first conductive pattern is a pillar pattern. A pad pattern having a square top surface is preferred. The length of one side of the pad pattern (the length of the short side in the case of a rectangular shape) is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, and even more preferably 0.5 to 10 μm. The thickness of the pad pattern is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, and even more preferably 0.2 to 2 μm.

[0038] The second conductive pattern may be in contact with the second insulating pattern, or may further include a second seed layer or the like between the second conductive pattern and the second insulating pattern.

[0039] [Second Seed Layer] The second member of the present invention may further include a second seed layer. The second seed layer is preferably present between the second insulating pattern and the second conductive pattern. Preferred aspects of the second seed layer are the same as those of the first seed layer of the first member described above.

[0040] [Distance from the surface of the second substrate to the surface of the second conductive pattern on the side opposite to the second substrate] In the second member of the present invention, the difference between the maximum and minimum distances from the surface of the substrate to the surface of the conductive pattern on the side opposite to the second substrate, in a direction perpendicular to the surface of the second substrate, is preferably 500 nm or less. Preferred aspects are the same as those of the first member described above.

[0041] [Second Pattern Angle] In the second member of the present invention, the angle formed between the bottom surface of the second conductive pattern and the side surface of the second conductive pattern (also referred to as the "second pattern angle") is preferably greater than 90° and not greater than 110°, but is not limited to this value. Preferred aspects are the same as the preferred aspects of the first pattern angle described above.

[0042] <Rewiring Layer> At least one of the first and second base materials preferably includes a rewiring layer.

[0043] (Semiconductor Device) The semiconductor device of the present invention is a device including the bonded structure of the present invention. Examples of the semiconductor device include the semiconductor device shown in FIG. 3 described below, or semiconductor devices in which one or more other components are mounted on these devices. That is, the semiconductor device of the present invention may be a device in which another component (such as a semiconductor chip) is further mounted on the bonded structure of the present invention. Examples of other semiconductor devices include processors (CPUs), 1 GHz-112 GHz band serializers, logic, accelerators (IPUs, TPUs, etc.), graphic processing units, volatile memories such as DRAMs (Dynamic Random Access Memory) and SRAMs (Static Random Access Memory), non-volatile memories such as flash memories, RF chips, silicon photonics chips, MEMS (Micro Electro Mechanical Systems), and sensor chips, and may be selected depending on the application. These semiconductor chips are preferably electrically connected to at least one of the first conductive pattern and the second conductive pattern in the bonded structure of the present invention.

[0044] 3A and 3B are schematic cross-sectional views showing an example of a bonded body of the present invention in which a first member and a second member are bonded. ２ A first insulating pattern 102 is formed on a first substrate 100 having a layer 100b made of a material selected from the group consisting of a silicon wafer 110a, a silicon substrate 110b, a silicon substrate 110c, a silicon substrate 110d, a silicon substrate 110e, a silicon substrate 110f, a silicon substrate 110g, a silicon substrate 110h, a silicon substrate 110h, a silicon substrate 110h, a silicon substrate 110i, a silicon substrate 110j, a silicon substrate 110m, a silicon substrate 110m, a silicon substrate 110m, a silicon substrate 110m, a silicon substrate 110m, a silicon substrate 110b ...c, a silicon substrate 110m, a silicon substrate 110m, a silicon substrate 110b, a silicon substrate ２ 3B shows a bonded body in which a second insulating pattern 112 is formed on a second substrate 110 having a layer 110b made of SiO 2 , and a second member having a first seed layer 114 and a first conductive pattern 116 formed in the area between the second insulating patterns 112 is bonded to the second member. ２A first member is formed on a first substrate 100 having a layer 100b made of a material of which a first insulating pattern 102 is formed, and a first seed layer 104 and a first conductive pattern 106 are formed in the regions between the first insulating patterns 102. A silicon wafer 110a is provided with a SiO ２ 3(c) shows a bonded body in which a second insulating pattern 120 made of an inorganic insulating film and a second member on which a second conductive pattern 122 is formed are bonded to a second base material 110 having a layer 110b made of an inorganic insulating film. ２ 1 shows a bonded structure in which a second insulating pattern 120 made of an inorganic insulating film and a second member on which a second conductive pattern 122 is formed are bonded onto a second base material 110 having a layer 110b made of an inorganic insulating film. However, the bonded structure of the present invention is not limited to these embodiments and may have other embodiments.

[0045] (Method for manufacturing bonded body) A method for manufacturing a bonded body of the present invention is a method for manufacturing a bonded body that bonds a first member having a first base material, a first insulating pattern arranged on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern arranged on the second base material, and a second conductive pattern present between the second insulating patterns, the method comprising: a conductive layer forming step of forming a conductive layer in regions between the first insulating patterns of the first base material and on the first insulating pattern, on which the first insulating pattern is formed, to obtain a member A; a polishing step of polishing the member A to obtain a first member having the first conductive pattern and the first insulating pattern exposed on its surface; and a joining step of joining the first member and a second member to obtain a member, wherein an angle formed between a bottom surface of the conductive pattern of at least the first member and a side surface of the conductive pattern is greater than 90° and equal to or less than 110°. According to the method for producing a bonded body of the present invention, the above-described bonded body of the present invention is produced.

[0046] Except for the fact that the first pattern angle before the joining is limited to greater than 90° and not greater than 110°, the preferred aspects of the first member (i.e., the preferred aspects of the first substrate, the first insulating pattern, the first conductive pattern, etc. included in the first member) are as described above, and these preferred aspects are also similar to the preferred aspects of the first member described above.

[0047] Furthermore, the method for producing a bonded body of the present invention preferably includes a film formation step, prior to the conductive layer formation step, of applying a first insulating pattern-forming composition to the substrate to form a film. It is more preferable that the method for producing a bonded body of the present invention includes a film formation step, prior to the conductive layer formation step, of applying a first insulating pattern-forming composition to the first substrate to form a film, and that the first insulating pattern-forming composition contains at least one compound selected from the group consisting of a photoradical polymerization initiator and a photoacid generator. Details of the first insulating pattern-forming composition will be described later. Furthermore, the method for producing a bonded body of the present invention preferably includes, after the film formation step, a drying step of drying the film, an exposure step of exposing the dried film to light, and a development step of developing the exposed film using a developer. In addition, the method for producing a bonded body of the present invention preferably includes a heating step after the film formation step.

[0048] <Film Forming Step> The method for producing a bonded body of the present invention preferably includes a film forming step, prior to the conductive layer forming step, of applying a first insulating pattern forming composition to the first base material to form a film. In particular, the method for producing a bonded body of the present invention preferably includes a film forming step, prior to the conductive layer forming step, of applying a first insulating pattern forming composition to the first base material to form a film, and the first insulating pattern forming composition preferably contains at least one compound selected from the group consisting of a photoradical polymerization initiator and a photoacid generator. Details of these components will be described later.

[0049] The i-line transmittance of a 3 μm thick film formed by heating the first insulating pattern-forming composition at 100° C. for 3 minutes is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. Details of the composition for forming a first insulating pattern will be described later.

[0050] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods 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 is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, 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 used in which a coating film formed by applying the coating composition to a temporary support using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which various solvents are applied to the substrate before applying the resin composition to improve the wettability of the substrate.

[0051] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a bonded body of the present invention may include a drying step of drying the film formed in the film-forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film 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 carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0052] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed. Selective exposure means that a portion of the film is exposed. In addition, selective exposure forms exposed regions (exposed portions) and unexposed regions (non-exposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0053] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0054] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. Exposure using a high-pressure mercury lamp is particularly preferred, and exposure using i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0055] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a bonded body of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 160°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0056] <Development Step> The film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a bonded body of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By performing development, one of the exposed and unexposed portions of the film is removed to form a pattern. Here, development in which the unexposed portions of the film are removed in the development step is called negative development, and development in which the exposed portions of the film are removed in the development step is called positive development.

[0057] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0058] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0059] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

[0387] of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0060] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0061] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0062] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0063] As the basic compound, from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. However, to promote the imidization reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferred that it is difficult for the amount remaining to decrease before heating due to vaporization, etc., is preferred. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C. The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100° C., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher. The developer may contain only one type of basic compound, or may contain two or more types.

[0064] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminobenzylamine, methyl ... ethane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0065] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0066] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the developer. The developer may contain only one type of basic compound or base generator, or two or more types. When two or more types of at least one of the basic compound and base generator are used, the total content thereof is preferably within the above-mentioned range.

[0067] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0068] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0069] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0070] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0071] Here, the first insulating pattern-forming composition was applied to a silicon wafer and heated at 100° C. for 180 seconds, and then 100 mJ / cm ２ and heated at 110°C for 3 minutes, the swelling rate of the film in the developer is preferably 15% by volume or less, more preferably 12% by volume or less, and even more preferably 10% by volume or less.

[0072] [Rinse Liquid] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0073] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse solution is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0074] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclopentanone or PGMEA.

[0075] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, and may also account for 100% by mass of the total mass of the rinse solution.

[0076] The rinse solution may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains the organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained when the developer contains an organic solvent, and the same applies to preferred embodiments. The basic compound and base generator contained in the rinse solution may be selected taking into consideration the solubility in the solvent in the rinse solution, etc.

[0077] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, the total content thereof is preferably within the above-mentioned range.

[0078] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0079] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using a spray nozzle. The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

[0080] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0081] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0082] The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator. Preferred aspects of the organic solvent and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent and at least one of the basic compound and the base generator used in the rinse liquid described above. The treatment liquid can be supplied to the pattern using the same method as the rinse liquid described above, and preferred aspects are also the same.

[0083] The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. There is no particular limitation on the lower limit of the content, but it is preferably, for example, 0.1% by mass or more. Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, relative to the total solid content of the treatment liquid. When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When there are two or more types of at least one of the basic compound and the base generator, it is preferable that the total amount thereof is within the above-mentioned range.

[0084] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a bonded body of the present invention may include a heating step in which the pattern obtained by the development step is heated. Furthermore, the heating step may be performed after the development step, such as after the conductive layer formation step described below or after the polishing step described below, and the timing of its execution is not particularly limited. Furthermore, the method for producing a bonded body of the present invention may include a heating step in which a pattern obtained by another method without a development step or a film obtained by a film formation step is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0085] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0086] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0087] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0088] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0089] Heating may be performed in two or more heating temperature stages. For example, the temperature may be increased from 25°C to 150°C at a rate of 5°C / min, held at 150°C for 60 minutes, increased from 150°C to 230°C at a rate of 5°C / min, and held at 230°C for 120 minutes. Heat treatment while irradiating with ultraviolet light, as described in U.S. Pat. No. 9,159,547, is also preferred. Such a pretreatment step can improve the film properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment step may be performed in two or more steps. For example, a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 230°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0090] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0091] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a bonded body of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a bonded body of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0092] <Conductive Layer Forming Step> The method for producing a bonded body of the present invention includes a conductive layer forming step of forming a conductive layer on the insulating patterns and in regions between the insulating patterns of the base material on which the insulating patterns have been formed, to obtain a member A. In the conductive layer forming step, the conductive layer can be formed by plating, applying a conductive paste, or the like. The maximum thickness of the conductive layer formed in the conductive layer forming step is not particularly limited, but is preferably 500 to 10,000 nm, and more preferably 1,000 to 5,000 nm.

[0093] The conductive layer forming step can be carried out by, for example, electrolytic copper plating. Here, it is also preferable to use filling plating to fill the areas between the insulating patterns. Alternatively, electroless copper plating may be used. These methods can be carried out by known methods.

[0094] The conductive layer formed in the conductive layer forming step is preferably present in the regions between the insulating patterns and on top of the insulating patterns, filling the regions between the insulating patterns and covering the insulating patterns. It is not necessary for the conductive layer to fill all of the regions between the insulating patterns; for example, the conductive layer may be formed along the inner walls (side and bottom surfaces) of these regions. In such an embodiment, polishing in the polishing step described below can be performed to remove regions not filled with the conductive layer or to flatten the surface of the member.

[0095] <First Seed Layer Formation Step> The method for producing a bonded body of the present invention preferably further includes a first seed layer formation step, prior to the conductive layer formation step, of forming a first seed layer (a power supply layer for electrolytic copper plating) in the region between the first insulating patterns. The first seed layer formation step is preferably a step of forming the first seed layer along the inner walls (side and bottom surfaces) of the region between the first insulating patterns. In addition, in the first seed layer formation step, the first seed layer may also be formed on the first insulating pattern. In such an embodiment, the first seed layer can be removed by polishing in the polishing step described below, ultimately exposing the first insulating pattern.

[0096] The first seed layer is formed by, for example, sputtering. Specifically, the first seed layer can be formed by using a metal such as titanium or chromium as a sputtering target and introducing oxygen, nitrogen, or the like as a reactive gas. These methods can be performed by known methods. Other known methods for forming the first seed layer may also be used.

[0097] The thickness of the first seed layer is preferably 5 to 400 nm, more preferably 10 to 300 nm, and even more preferably 20 to 250 nm. The first seed layer may be formed of two or more layers. When the first seed layer is formed of two or more layers, it is preferable that the thickness of each layer is within the above range. For example, after forming a first seed layer made of titanium, chromium, nickel, or the like as the first layer, a second first seed layer made of a metal used in conductive layers, such as copper, may be formed by plating or the like. From the viewpoint of improving adhesion and reliability, it is preferable to form two or more seed layers.

[0098] <Polishing Step> The method for producing a bonded body of the present invention includes a polishing step of polishing member A to obtain a member having the first conductive pattern and the first insulating pattern exposed on the surface.

[0099] The polishing step is a step of polishing member A to obtain a member in which the first conductive pattern and the first insulating pattern are exposed. The polishing step removes the surface of the conductive layer to form the first conductive pattern. Furthermore, if a first seed layer is formed on the first insulating pattern by the above-mentioned method, it is preferable that the first seed layer on the first insulating pattern is also removed. The polishing 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), more preferably CMP. The slurry used for the CMP is not particularly limited, but examples include silica slurry, ceria slurry, alumina slurry, titania slurry, zirconia slurry, germania slurry, manganese oxide slurry, and diamond slurry. The particle size of the slurry is not particularly limited, but from the viewpoint of preventing scratches, an average particle size of 1000 nm or less is preferable, an average particle size of 500 nm or less is more preferable, and an average particle size of 200 nm or less is even more preferable. Although there is no particular lower limit to the particle size of the slurry, it is preferably 10 nm or more from the viewpoint of the polishing rate. Furthermore, these methods may be combined, such as by performing CMP after cutting.

[0100] Commercially available silica slurries include, for example, NP6220, NP6502, NP6504, NP6610, NP6605, NP8020H, NP8020, NP8030, NP8040, NP8040W, and EG1103 (all manufactured by Nitta DuPont). Commercially available CMP slurries for Cu include, for example, CSL9044C, CSL9400C, CSL9500C, and CSL9215C (manufactured by Fujifilm Electronic Materials Co., Ltd.). Commercially available CMP slurries for barrier metals, such as those used for seed layers, include, for example, BSL8180C, BSL8400C, BSL8250C, BSL8300C, and FSL1531C (manufactured by Fujifilm Electronic Materials Co., Ltd.).

[0101] The content of particles such as silica, ceria, and alumina in the slurry is not particularly limited, but from the viewpoint of suppressing scratches, etc., it is preferably 0.01 to 80 mass% relative to the total mass of the slurry, more preferably 0.1 to 70 mass%, and even more preferably 0.2 to 60 mass%. In this specification, the content of each component in the slurry is described as the content of each component when the slurry is used for polishing. When the slurry is diluted with water or a solvent during polishing, it is the content in the diluted composition. Furthermore, as the particles, two types of particles made of different materials may be used in combination, or two types of particles with different particle sizes may be used in combination. In these cases, it is preferable that the total content of the particles contained falls within the above-mentioned numerical range.

[0102] [Oxidizing Agent] The slurry preferably contains an oxidizing agent. It is believed that the oxidizing agent acts on the surface of the insulating pattern, making the insulating pattern more easily removable and increasing the etching rate. Examples of oxidizing agents include hydrogen peroxide, peroxides, nitrates, iodates, periodates, hypochlorites, chlorites, chlorates, perchlorates, persulfates, dichromates, permanganates, ozone water, silver (II) salts, and iron (III) salts.

[0103] The amount of oxidizing agent used is preferably 0.0001 to 20 mol, more preferably 0.001 to 15 mol, and even more preferably 0.001 to 10 mol per 1 L of slurry during use. Two or more oxidizing agents may be used in combination. In this case, it is preferable that the total content of the oxidizing agents contained falls within the above numerical range.

[0104] [pH Adjuster] The slurry preferably contains a pH adjuster. By containing a pH adjuster, the pH can be kept constant during polishing, thereby suppressing variations in polishing. Examples of pH adjusters include acidic compounds, alkaline compounds, pH buffers, etc., and it is preferable to contain an alkaline compound.

[0105] As the acidic compound, an inorganic acid can be used. Examples of the inorganic acid include, but are not limited to, sulfuric acid, nitric acid, boric acid, and phosphoric acid. Among these inorganic acids, sulfuric acid, nitric acid, and phosphoric acid are preferably used.

[0106] Examples of alkaline compounds include ammonium hydroxide, organic ammonium hydroxides such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TMAH), ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methyl-2-methyl-1,6-hexanediamine), and the like. Examples of the amino acid salt include, but are not limited to, amine compounds such as (tris(ethoxyethyl)amine), alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycyl salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts, and lysine salts.

[0107] Examples of pH buffers include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and ammonium hydroxide. Other examples include amino acids and amino acid derivatives such as glycine, alanine, and N-methylglycine, and organic acids such as butyric acid and glycolic acid. However, usable pH buffers are not limited to these.

[0108] The amount of pH adjuster added is not particularly limited as long as it is an amount that can adjust the pH of the slurry to a target value, and the compound and amount added can be adjusted appropriately depending on the purpose. The pH can be selected arbitrarily, but in some cases, it may be preferable to adjust the pH to the alkaline side of 8 to 14, for example, in terms of the polishing rate, etc. It is also possible to prepare a slurry at a low pH, and the optimal pH can be selected appropriately taking into account the polishing rate, the antiseptic properties of adjacent metals, etc.

[0109] [Corrosion inhibitor] The slurry preferably contains a corrosion inhibitor. By containing a corrosion inhibitor, for example, it is possible to suppress corrosion of metal (e.g., copper) in the conductive pattern. Examples of the corrosion inhibitor include heteroaromatic ring compounds. Furthermore, the corrosion inhibitor is preferably a compound that forms a passivation film on the metal surface to be polished.

[0110] A "heteroaromatic ring compound" is a compound having a ring structure containing one or more heteroatoms as ring members. The heteroatom is preferably a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, more preferably a nitrogen atom, a sulfur atom, an oxygen atom, or a selenium atom, particularly preferably a nitrogen atom, a sulfur atom, or an oxygen atom, and most preferably a nitrogen atom or a sulfur atom. The heteroaromatic ring compound is not particularly limited, but examples thereof include the compounds described in paragraphs 0027 to 0035 of JP 2009-224695 A.

[0111] The content of the corrosion inhibitor is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.0005 to 0.05 mol per liter of the slurry. Two or more corrosion inhibitors may be used in combination. In this case, it is preferable that the total content of the corrosion inhibitors contained falls within the above numerical range.

[0112] [Other Additives] The slurry may contain various known additives depending on the purpose. Known additives include, but are not limited to, surfactants, solvents, chelating agents, etc.

[0113] -Surfactant- The slurry preferably contains a surfactant. The inclusion of a surfactant may have the effect of protecting the metal film and suppressing excessive polishing. Examples of surfactants include anionic, cationic, nonionic, and amphoteric (betaine) surfactants. These surfactants are not particularly limited, but examples include the compounds described in paragraphs 0038 to 0047 of JP 2009-224695 A.

[0114] The amount of surfactant added is preferably 0.0001 to 10 g, more preferably 0.0005 to 5 g, and particularly preferably 0.0005 to 3 g, per liter of slurry. Two or more surfactants may be used in combination. In this case, it is preferable that the total content of the surfactants contained falls within the above numerical range.

[0115] -Solvent- The slurry may contain a solvent. Examples of the solvent include water and organic solvents. Examples of the organic solvent include polar solvents such as alcohol and acetic acid. For the purpose of improving the wettability to the surface to be polished and bringing the polishing rates of the interlayer insulating film and the barrier film closer together, examples of the solvent include glycols, glycol monoethers, glycol diethers, alcohols, carbonates, lactones, ethers, ketones, phenols, dimethylformamide, n-methylpyrrolidone, ethyl acetate, ethyl lactate, sulfolane, and sulfoxides. Among these, at least one solvent selected from dimethyl sulfoxide, glycol monoethers, alcohols, and carbonates is preferred.

[0116] The solvent may be supplied during polishing, or may be added to the slurry before polishing. The amount of solvent used may be appropriately determined taking into consideration the state of the surface to be polished. When an organic solvent is added, the content of the organic solvent is preferably 0.01 to 90 parts by mass per 100 parts by mass of the slurry used during polishing. The content is more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, in order to improve the wettability of the slurry to the substrate during polishing. Furthermore, the upper limit is more preferably 50 parts by mass or less, and even more preferably 10 parts by mass or less, in order to facilitate the manufacturing process.

[0117] The polishing may be performed to the extent that the portion of the conductive layer formed on the first insulating pattern and the first seed layer, if any, are removed to expose the conductive layer and the first insulating pattern, but may also be performed to the extent that the top surface of the first insulating pattern is polished. In this manner, the flatness of the surface of the first member may be improved.

[0118] Here, for example, when the above-mentioned first seed layer is present, polishing may be performed in two stages. Specifically, in a first stage, polishing is performed down to the surface of the first seed layer to remove the conductive layer and expose the first seed layer, and then in a second stage, polishing is performed to remove the first seed layer and expose the insulating pattern.

[0119] The difference between the maximum and minimum distances from the first substrate to the surface of the conductive pattern on the opposite side from the substrate after polishing is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.

[0120] <Dicing Step> The method for producing a bonded body of the present invention may include a dicing step of dicing the first member into individual pieces.

[0121] <Other Steps> The method for producing a bonded body of the present invention may further include other steps known in the art when producing the first member.

[0122] <Example of Manufacturing First Member> An example of manufacturing a first member in the method for manufacturing a bonded body of the present invention will be described below with reference to the drawings. In each drawing, duplicated reference numerals that have already been explained may be omitted. Also, the dimensional ratios of each member in the drawings may not be accurate. The second member can also be manufactured by a method similar to the method described below. FIG. 4 is a process explanatory diagram showing, in cross section, a schematic process of a method for manufacturing a first member according to one embodiment of the present invention. FIG. 4(a) shows a method for manufacturing a first member by depositing SiO 2 on a silicon wafer 100a. ２ 4(b) shows a state in which a first insulating pattern 102 is formed on a first substrate 100 having a layer 100b made of. The first insulating pattern 102 has regions 103 between the first insulating patterns. FIG. 4(b) shows a state in which a first seed layer 104 and a conductive layer 105 are formed on the regions 103 between the first insulating patterns and on the first insulating pattern 102 in FIG. 4(a). FIG. 4(b) shows a state in which the member A described above is formed. FIG. 4(c) shows a state in which the member A shown in FIG. 4(b) has been polished to form the first insulating pattern 102 and a first conductive pattern 106.

[0123] <Another Example of Manufacturing the First Member> Hereinafter, another example of manufacturing the first member of the present invention will be described with reference to the drawings. In each drawing, duplicated reference numerals that have already been explained may be omitted. In addition, the dimensional ratios of each member in the drawings may not be accurate. The second member can also be manufactured by a method similar to the method described below. FIG. 5 is a process explanatory diagram showing, in a schematic cross-sectional view, another example of the process (part) of the method for manufacturing the first member according to the method for manufacturing a bonded body of the present invention. FIG. 5(a) shows a state in which SiO 2 is deposited on a silicon wafer 2a. ２ 5(b) shows a substrate 1 having an insulating pattern 4 and a conductive pattern 6 formed on a substrate 2 including a layer 2b made of a material such as a silicon dioxide powder. Such a substrate can be manufactured by a conventional method or can be obtained commercially. FIG. 5(b) shows a state in which a photosensitive resin composition used to form a first insulating pattern is applied to the substrate 1 to form a film 10. FIG. 5(c) shows a state in which the film 10 in FIG. 5(b) is exposed and developed to form a line-and-space pattern 12, resulting in a first insulating pattern 14 before curing. FIG. 5(d) shows a state in which a first seed layer 42 is formed on the first insulating pattern 14 with the line-and-space pattern 12 formed thereon. FIG. 5(e) shows a state in which a conductive layer 44 is formed on the first seed layer 42 formed in FIG. 5(d). The conductive layer 44 may be manufactured by a conventional method such as sputtering or plating. As described above, the conductive layer 44 may be a layer composed of multiple layers, such as a conductive pattern including, in this order, a titanium layer formed by sputtering, a copper layer formed by sputtering, and a copper layer formed by plating, or a conductive pattern including, in this order, a titanium layer formed by sputtering, a copper layer formed by sputtering, and a tin layer formed by plating. Figure 5( f ) shows the state after the member A shown in Figure 5( e ) has been polished to form the first conductive pattern 46. Here, polishing may be performed multiple times, and different slurries may be used in each of the multiple polishing steps.

[0124] <Step of Producing a Second Member> The method for producing a bonded body of the present invention may further include a step of producing a second member. The step of producing the second member is a step of producing a second member including a second base material, a second insulating pattern present on the second base material, and a second conductive pattern that provides electrical conduction between the second insulating patterns, and preferably includes steps A to C. Step A: A second preparation step of preparing member A2, which is a second base material on which the second insulating pattern is formed; Step B: A second conductive layer formation step of forming a second conductive layer in the areas between the second insulating patterns of member A2 and on the second insulating pattern to obtain member B2; Step C: A second polishing step of polishing member B2 to obtain a second member in which the second conductive pattern and the second insulating pattern are exposed. According to the step of producing a second member of the present invention, the above-mentioned second member is produced. That is, the preferred aspects of the second substrate, the second insulating pattern, the second conductive pattern, and the angle formed between the bottom surface of the second conductive pattern of the second member and the side surface of the second conductive pattern (second pattern angle before bonding) in the second member to be manufactured are the same as the preferred aspects of these in the second member described above.

[0125] [Step A] The step of producing the second member of the present invention preferably includes a preparation step (step A) of preparing a member A2 including the second insulating pattern. In the preparation step, the member A2 may be produced by a known method or may be obtained by means such as purchase. A manufacturing method for producing the member A2 will be described below.

[0126] The method for producing member A2 preferably includes a second film formation step of applying a photosensitive resin composition (second insulating pattern-forming composition) to a substrate to form a film, a second exposure step of selectively exposing the film formed in the second film formation step, and a second development step of developing the film exposed in the second exposure step with a developer to form a second insulating pattern. Details of each step are described below. Details of each photosensitive resin composition (hereinafter also simply referred to as "resin composition") will be described later.

[0127] The step of producing the second member preferably includes a second film-forming step of applying a photosensitive resin composition to a second substrate to form a film. The second substrate in the second film-forming step is as described above.

[0128] The details and preferred aspects of the second film-forming step are the same as those of the first film-forming step described above. Furthermore, the process for producing the second member may include a second drying step after the second film-forming step. The details and preferred aspects of the second drying step are the same as those of the drying step described above.

[0129] The film formed in the second film-forming step may be subjected to a second exposure step in which the film is selectively exposed to light. The second exposure step can be performed in the same manner as the exposure step in the above-described method for producing a bonded structure of the present invention, and preferred embodiments are also similar.

[0130] The film after the second exposure step may be subjected to a step of heating after exposure (second post-exposure baking step). The second post-exposure baking step can be performed by the same method as the post-exposure baking step in the above-mentioned method for producing a bonded body of the present invention, and preferred embodiments are also the same.

[0131] - Second Development Step - The film after exposure may be subjected to a second development step in which the film is developed using a developer to form a pattern. The second development step can be performed in the same manner as the development step in the above-mentioned method for producing a bonded structure of the present invention, and preferred embodiments are also the same.

[0132] - Second Heating Step - The film developed in the second developing step may be subjected to a second heating step in which the film is heated. The second heating step may be performed in the same manner as the heating step in the above-described method for producing a bonded body of the present invention, and the preferred embodiments are also the same. This heating may be performed before or after the polishing step after the second conductive layer forming step.

[0133] - Second Post-Treatment Step - After the second development step, a second post-treatment step may be performed in which post-treatment is carried out by at least one of heating and exposure. The heating temperature is preferably 100 to 160°C, and more preferably 120 to 160°C. The exposure is carried out at 1,000 to 50,000 mJ / cm by the same method as in the second exposure step described above. ２ and a method of exposing the entire surface with an exposure amount of 1000 ppm.

[0134] [Step B] The step of producing the second member preferably includes a second conductive layer formation step of forming a second conductive layer in the region between the second insulating patterns of member A2 and on the second insulating pattern to obtain member B2. Step B can be performed by a method similar to the conductive layer formation method in the above-mentioned method of producing a joined body of the present invention, and the preferred embodiments are also similar.

[0135] [Second Seed Layer Formation Step] The process for manufacturing the second member preferably further includes a second seed layer formation step of forming a seed layer present in the region between the patterns between steps A and B. The second seed layer formation step is preferably a step of forming a second seed layer along the inner walls (side and bottom surfaces) of the region between the patterns. In this embodiment, the second seed layer can be removed by polishing in step C described below, finally exposing the second insulating pattern.

[0136] The second seed layer forming step can be performed by the same method as the seed layer forming step in the above-described method for producing a bonded body of the present invention, and the preferred embodiments are also the same.

[0137] [Step C] The step of producing a second member includes, as step C, a polishing step of polishing member B to obtain a second member in which the second conductive pattern and the second insulating pattern are exposed. The polishing step removes the surface of the conductive layer to form the second conductive pattern. Furthermore, if a second seed layer is formed by the above-described method, it is preferable that the second seed layer is also removed. The polishing step can be performed by the same method as the polishing step in the above-described method of producing a bonded body of the present invention, and the preferred embodiments are also similar.

[0138] [Second Dicing Step] The step of manufacturing the second member may include a second dicing step of dicing the second member into individual pieces.

[0139] [Other Steps] The step of manufacturing the second member may further include other steps known in the art.

[0140] <Rewiring Layer> At least one of the first and second base materials preferably includes a rewiring layer.

[0141] <Bonding Step> The method for producing a bonded body of the present invention includes a bonding step of bonding a surface of the first member having the first insulating pattern and the first conductive pattern to a surface of the second member having the second insulating pattern and the second conductive pattern. The first insulating pattern and the second insulating pattern are preferably mirror-symmetric, but may have a partial non-mirror symmetry. The first conductive pattern and the second conductive pattern are preferably mirror-symmetric, but may have a partial non-mirror symmetry. When the first insulating pattern of the first member has a polyimide-containing portion or a polyimide-containing precursor portion and the insulating pattern of the second member is an inorganic insulating film such as SiN, the bonding step is a step of bonding a surface of the first member having the polyimide or polyimide-containing precursor portion to a surface of the second member having the inorganic insulating film such as SiN. The polyimide-containing portion refers to a portion of the first insulating pattern or the second insulating pattern that contains polyimide, in whole or in part. The polyimide-containing precursor portion refers to a portion of the first insulating pattern or the second insulating pattern that contains a polyimide precursor, which is part or all of the first insulating pattern or the second insulating pattern. The polyimide-containing precursor portion is preferably formed from a photosensitive resin composition containing a polyimide precursor. The polyimide-containing portion is preferably formed from a photosensitive resin composition containing a polyimide or a polyimide precursor, or a photosensitive resin composition containing a polyimide. Here, in the polyimide-containing portion, the polyimide precursor is preferably converted to polyimide by heating.

[0142] The bonding electrically bonds the first conductive pattern on the first member and the second conductive pattern on the second member. In one preferred aspect of the present invention, in the bonding step, the first conductive pattern and the second conductive pattern are bonded so as to be in direct contact with each other.

[0143] The bonding is preferably performed by a method including heating, and more preferably by a method including heating and pressure. The temperature during bonding (bonding temperature) is preferably 100°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. The upper limit is preferably 450°C or lower, more preferably 400°C or lower, even more preferably 380°C or lower, particularly preferably 350°C or lower, even more preferably 300°C or lower, even more preferably 280°C or lower, even more preferably 260°C or lower, and particularly preferably 250°C or lower. As described above, this temperature is preferably a temperature near the melting point of at least one of the conductive patterns, taking into consideration that the conductive patterns (first conductive pattern or second conductive pattern) are melted to enable bonding between the electrodes. However, if the oxide film on the surface of the conductive pattern is removed, bonding is possible even at a temperature below the melting point. The heating time in the bonding process is not particularly limited, but is preferably 5 seconds or higher, more preferably 1 minute or higher, and even more preferably 2 minutes or higher. The upper limit is practically 30 minutes or less. The heating environment is not particularly limited, but it is preferable to perform the heating in a reduced pressure atmosphere while mechanically pressurizing the first insulating pattern and the second insulating pattern. The atmospheric pressure is 1×10 －５ Preferably, it is 1×10 mbar or more. －４ More preferably, it is 5×10 mbar or more. －４ The upper limit is preferably 0.1 mbar or less, and more preferably 1 × 10 －２ More preferably, it is 5×10 mbar or less. －３It is more preferable that the pressure is 100 kN or less. The joining step is preferably performed by sandwiching two members (a first member and a second member), and it is preferable that pressure is applied to the members at this time. The pressure applied to the members is preferably 1 kN or more, more preferably 5 kN or more, and even more preferably 10 kN or more. A practical upper limit is 100 kN or less. There are no particular restrictions on the equipment used in the joining step, but equipment used for joining or reflowing electronic components can be suitably used.

[0144] Furthermore, in the bonding step, when the first member includes a polyimide-containing portion or a polyimide-containing precursor portion, it is also preferable that the temperature of the first member be preheated to 70°C or higher. When the second member includes a polyimide-containing portion or a polyimide-containing precursor portion, it is also preferable that the temperature of the second member be preheated to 70°C or higher. The above temperature is preferably 70°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit of the above temperature is not particularly limited, but is preferably 180°C or lower. This aspect can reduce the takt time of the bonding process. Furthermore, the fluidity of the first insulating pattern or the second insulating pattern (particularly the polyimide-containing portion or the polyimide-containing precursor portion) during bonding is improved, which may improve the maximum peel resistance.

[0145] It is preferable that the polyimide-containing precursor portion becomes a polyimide-containing portion by the joining step. Here, when both the first member and the second member have a polyimide-containing portion or a polyimide-containing precursor portion, the interfaces may be joined by the joining step to form one polyimide-containing portion.

[0146] The polyimide-containing portion after the bonding step is preferably an insulating member. The insulating property (electrical resistance) of the polyimide-containing portion is not particularly limited, but the volume resistivity is preferably 1×10 １５ It is preferable that the resistance is Ω cm or more, and 1×10 １６ It is more preferable that the resistivity is Ω cm or more. There is no particular upper limit, but it is preferably 1×10 １９In practice, the dielectric strength is Ω·cm or less. The breakdown voltage is preferably 1 kV / mm or more, and more preferably 10 kV / mm or more. There is no particular upper limit, but in practice, the dielectric strength is 1000 kV / mm or less. In this specification, the measurements of the volume resistivity and the breakdown voltage are in accordance with JIS C2151:2006 and JIS C2318:2007.

[0147] Furthermore, the glass transition temperature of the polyimide-containing portion after the bonding step is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 230° C. or lower. There is no particular limitation on the lower limit of the glass transition temperature, but it is preferably 120° C. or higher.

[0148] The difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 5% or more, more preferably 6% or more. Another preferred embodiment of the present invention is one in which the difference in cyclization rate is 10% or more. In the present invention, the cyclization rate of the polyimide is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1370 cm-1, which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1370 cm-1. The obtained peak intensities P1 and P2 can be used to determine the cyclization rate of the polyimide based on the following formula: Cyclization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0149] The cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%. The cyclization rate of the polyimide in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 91 to 100%, more preferably 94 to 100%, and even more preferably 97 to 100%.

[0150] When the second member includes a polyimide-containing precursor portion, the difference between the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of the polyimide contained in the polyimide-containing portion formed at the bonded portion after the bonding step is preferably 5% or more, more preferably 6% or more. Another preferred aspect of the present invention is that the difference in cyclization rate is 10% or more. When the second member includes a polyimide-containing precursor portion, the cyclization rate of the polyimide in the polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%.

[0151] <Annealing Step> The annealing step is a heating step that may be incorporated after the bonding step (e.g., bonding using a flip-chip bonder). The annealing step can increase the peel resistance of the bonded portion. The heating means is not particularly limited, and heating devices such as a hot plate or an oven can be used. The heating temperature in the annealing step is preferably a temperature equal to or lower than the bonding temperature in the bonding step. The heating temperature in the annealing step is preferably 180 to 440°C, more preferably 200 to 350°C, and even more preferably 210 to 260°C. The heating temperature in the annealing step may also be determined taking into account the bonding temperature in the bonding step and the heating temperature in the heating step. The difference between the bonding temperature in the bonding step and the heating temperature in the annealing step (bonding temperature in the bonding step - heating temperature in the annealing step) is preferably 10°C or more. The upper limit is not particularly limited, but is preferably 250°C or less, and more preferably 200°C or less. When the above-mentioned heating step is performed, the heating temperature in the annealing step is preferably a temperature equal to or higher than the heating temperature in the above-mentioned heating step (maximum heating temperature). The difference between the heating temperature in the annealing step and the heating temperature in the heating step (heating temperature in the annealing step - heating temperature in the heating step) is preferably 10°C or more, more preferably 30°C or more. There is no particular upper limit, but for example, it is preferably 250°C or less, more preferably 150°C or less. The heating time in the annealing step is preferably equal to or longer than the bonding time in the bonding step. The heating time in the annealing step (heating time at the above heating temperature) is preferably 30 minutes or more. There is no particular upper limit, but it is preferably 10 hours or less, more preferably 3 hours or less. The difference between the heating time in the annealing step and the heating time in the bonding step (heating time in the annealing step - heating time in the bonding step) is preferably 10 minutes or more. There is no particular upper limit, but it is preferably 10 hours or less, more preferably 3 hours or less. The heating atmosphere is air, N ２The ambient pressure can be appropriately selected from those available for heating equipment, such as under pressure or under vacuum. The atmospheric pressure is not particularly limited, but is preferably 1 atmosphere or less, and more preferably within 1 atmosphere ±0.1 atmosphere. 1 atmosphere means 101,325 Pa. For example, the annealing step can be performed under atmospheric pressure without applying pressure or vacuum. The imidization rate after the annealing step is preferably, for example, 98% or more. There is no particular upper limit, and it is preferably, for example, 100%.

[0152] <Other Steps> The method for manufacturing a bonded body of the present invention may further include other steps known in the art. The method for manufacturing a member of the present invention does not preclude the inclusion of other steps between the steps defined above. While the bonding step has been described mainly as an example in which a first member and a second member are bonded face-to-face, it is also possible to use a configuration in which multiple first members are arranged in parallel and bonded to the second member. Alternatively, a configuration in which multiple first members, each having an insulating pattern and a conductive pattern formed on its back surface, are stacked and bonded to the second member may also be used.

[0153] (Photosensitive Resin Composition) Hereinafter, the photosensitive resin composition used to form the first insulating pattern (first insulating pattern-forming composition) and the photosensitive resin composition used to form the second insulating pattern (second insulating pattern-forming composition) in the method for producing a bonded body of the present invention will be described in detail. These compositions are sometimes simply referred to as "photosensitive resin compositions." The first insulating pattern-forming composition and the second insulating pattern-forming composition may have the same composition, or may have different compositions. The photosensitive resin composition of the present invention is a photosensitive resin composition used to form the first insulating pattern used in the method for producing a bonded body of the present invention. Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

[0154] <Specific Resin> The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure. In the present invention, the term "main chain" refers to the relatively longest bonded chain in the resin molecule, and the term "side chain" refers to any other bonded chain. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin refers to a resin whose chemical structure changes upon external stimulation to become a cyclized resin. Resins whose chemical structure changes upon heating to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction upon heating to form a ring structure to become a cyclized resin are more preferred. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition preferably contains a polyimide or a polyimide precursor as the specific resin. The specific resin preferably has a polymerizable group, more preferably a radically polymerizable group. When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably a radical polymerization initiator and a radical crosslinking agent. It may further contain a sensitizer as needed. From such a resin composition, for example, a negative-type photosensitive film is formed. Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.

[0155] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2). In formula (2), A １ and A２ are each independently an oxygen atom or —NR ｚ represents -, and R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R ｚ represents a hydrogen atom or a monovalent organic group.

[0156] A in formula (2) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. １１１ represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. R in formula (2) １１１ Examples of the group include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred, where each Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0157] R １１１is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, R １１１ is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0158] In the formula, A represents a single bond or a divalent linking group, and is selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, and —SO ２ -, -NHCO-, or a group selected from a combination thereof, and is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - is more preferably a group selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ In the formula, * represents a bonding site to another structure.

[0159] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3 ,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane parafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl can be mentioned.

[0160] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0161] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0162] R １１１ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film, wherein each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ The aliphatic hydrocarbon group here is preferably an alkylene group.

[0163] Also, R １１１From the viewpoint of i-line transmittance, it is preferable that is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that is a divalent organic group represented by formula (61). Formula (51) In formula (51), R ５０ ~R ５７ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of R is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). In formula (61), R ５８ and R ５９ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site 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 alone or in combination of two or more.

[0164] Also, R １１１ is also preferably a group represented by the following formula (71). １１１ is more preferably a group represented by the following formula (72). In formula (71), A １ ~A ３ are each independently a single bond or a divalent linking group, * represents a bonding site to the nitrogen atom in formula (2), and each of the four benzene rings described in formula (71) may have a substituent. In formula (72), * represents a bonding site to the nitrogen atom in formula (2).

[0165] In formula (71), A１ ~A ３ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, —S(═O) ２ -, -NHC(=O)-, or a group consisting of a combination of two or more thereof is preferred, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, or a group consisting of a combination of two or more thereof is more preferred, and an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O- is even more preferred. １ and A ３ is preferably —O—. ２ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. １ and A ３ is —O—, and A ２ -C(CH ３ ) ２ The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4. Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, among which -C(CH ３ ) ２ - is preferred. Examples of the substituents on the four benzene rings described in formula (71) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. An embodiment in which all of the four benzene rings described in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

[0166] Also, R １１１ is also preferably a group represented by the following formula (81). １１１is more preferably a group represented by the following formula (82). In formula (81), A １ and A ２ are each independently a single bond or a divalent linking group, * represents a bonding site to the nitrogen atom in formula (2), and the three benzene rings described in formula (81) may each have a substituent. In formula (82), * represents a bonding site to the nitrogen atom in formula (2).

[0167] In formula (81), A １ and A ２ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, —S(═O) ２ -, -NHC(=O)-, or a group consisting of a combination of two or more thereof is preferred, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, or a group consisting of a combination of two or more thereof is more preferred, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O- is even more preferred, and -C(CH ３ ) ２ It is particularly preferred that -.

[0168] R in formula (2) １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. In formula (5), R １１２ represents a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ -, -NHCO-, and a group selected from a combination thereof are preferred, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ )２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0169] Also, R １１５ is also preferably a group represented by the following formula (7). １１５ is more preferably a group represented by the following formula (7-2). In formula (7), A １ ~A ３ are each independently a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (2), and each of the four benzene rings described in formula (7) may have a substituent. In this specification, a bond crossing a side of a ring structure means that it substitutes one of the hydrogen atoms in the ring structure. In formula (7-2), * represents a bonding site with the carbonyl group in formula (2).

[0170] In formula (7), A １ ~A ３ and a preferred embodiment of the substituent on the benzene ring is A in the above formula (71). １ ~A ３ and the preferred embodiments of the substituents on the benzene ring are the same as those.

[0171] Also, R １１５ is also preferably a group represented by the following formula (8). １１５ is more preferably a group represented by the following formula (8-2). In formula (8), A ４ and A ５ are each independently —C(═O)—O— or —C(═O)NH—, and L １ is a divalent linking group, * represents a bonding site with the carbonyl group in formula (2), and the two benzene rings described in formula (8) may each have a substituent. ４ and A ５In a preferred embodiment of the present invention, one of the carbon atoms in the -C(=O)-O- group is -C(=O)-O- and the other is -C(=O)NH-. The orientation of the -C(=O)-O- group is not particularly limited, but the carbon atom in the -C(=O)-O- group may be L. １ It is preferable that the carbon atom in the —C(═O)—NH— is bonded to L via a single bond without a linking group. １ It is preferable that L is bonded to L via a single bond without a linking group. １ is preferably a hydrocarbon group which may have a substituent, more preferably an aromatic hydrocarbon group, and even more preferably a phenylene group. １ The hydrocarbon group in formula (8-2) may have a substituent. Examples of the substituent include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In formula (8-2), each R independently represents a substituent, n is an integer of 0 to 4, and * represents the bonding site with the carbonyl group in formula (2). Each R independently represents preferably a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, more preferably a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. n is preferably an integer of 0 to 2. An embodiment in which n is 2 is also one of the preferred embodiments of the present invention.

[0172] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５ The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). In formula (O), R １１５ represents a tetravalent organic group. １１５ is R in formula (2) １１５ The same applies to the preferred range.

[0173] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 2,3,3',4'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0174] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0175] In formula (2), R １１１ and R １１５ At least one of R may have an OH group. １１１Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0176] R in formula (2) １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. １１３ and R １１４ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R １１３ and R １１４ It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), with a group represented by the following formula (III) being preferred.

[0177]

[0178] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), 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. ２０１Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) 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 a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy 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 polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0179] In formula (2), R １１３is a hydrogen atom, or R １１４ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0180] In formula (2), R １１３ and R １１４ At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group. Preferred examples include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0181] The polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0182] Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0183] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ each independently represents a divalent organic group; R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R １１３ and R １１４ At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0184] A １ , A ２ , R １１１ , R １１３ and R １１４ are each independently A in formula (2). １ , A ２ , R １１１ , R １１３ and R １１４ The same definition and preferred range are also true. １１２ is R in formula (5). １１２ The same applies to the preferred range.

[0185] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of formula (2).

[0186] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0187] 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 dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are each within the above-mentioned ranges.

[0188] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23°C. From the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferred, and a polyimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. From the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0189] -Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a fluorine atom. The fluorine atom is, for example, R １３２ or R in the repeating unit represented by formula (4) described below １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３２ or R in the repeating unit represented by formula (4) described below １３１ The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

[0190] -Silicon Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described later. １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３１ It is more preferable that the silicon atom or the organic modified (poly)siloxane structure described below is contained in the polyimide. The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.

[0191] - Ethylenically unsaturated bond - From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have the ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable that the ethylenically unsaturated bond is in a side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is formed by the R １３２ or R １３１ and R １３２ or R １３１ Among these, the ethylenically unsaturated bond is more preferably contained as a group having an ethylenically unsaturated bond in R １３１ and R １３１ Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV):

[0192]

[0193] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0194] In formula (IV), R ２１ represents an alkylene group having 2 to 12 carbon atoms, —O—CH ２ CH(OH)CH ２-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of repeating alkyleneoxy groups is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms), or a group combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, or alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0195] Among these, R ２１ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1). In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R ２１ In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R in formula (IV). ２１The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0196] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0197] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0198] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of the polymerizable group other than a group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. Examples of the polymerizable group other than a group having an ethylenically unsaturated bond include R in the repeating unit represented by formula (4) below. １３１ The amount of polymerizable groups other than groups having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0199] - Polarity conversion group - The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is R １１３ and R １１４ The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ , contained in the terminals of polyimides, etc.

[0200] -Acid Value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. When the polyimide is subjected to development using a developer containing an organic solvent as a main component (e.g., "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid group contained in the polyimide preferably has a pKa of 0 to 10, and more preferably 3 to 8. pKa refers to the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa refers to a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. For pKa, reference may be made to the value listed in the "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.

[0201] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have the phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group can be, for example, R in the repeating unit represented by formula (4) described below. １３２ or R １３１ The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0202] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4). In formula (4), R １３１ represents a divalent organic group, and R １３２ represents a tetravalent organic group. When the compound has a polymerizable group, the polymerizable group is １３１ and R １３２ or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2): In formula (4-1), R １３３ is a polymerizable group, and the other groups have the same meanings as in formula (4). R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0203] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond and a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond. １３１ represents a divalent organic group. The divalent organic group is R １１１ The same examples as those listed above are given, and the preferred ranges are also the same. １３１The diamine residues include those remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. １１１ Examples include:

[0204] R １３１ is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0205] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN 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.

[0206] R １３２ represents a tetravalent organic group. The tetravalent organic group is R １１５ Examples of the group R are the same as those of the group R, and the preferred ranges are also the same. １１５ The four bonds of the tetravalent organic group exemplified by: are bonded to the four —C(═O)— moieties in formula (4) to form a condensed ring.

[0207] R １３２ Specific examples of R in the formula (2) of the polyimide precursor include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. １１５ From the viewpoint of the strength of the organic film, R １３２is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0208] R １３１ and R １３２ It is also preferable that at least one of R １３１ Preferred examples of R include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18). １３２ As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0209] The polyimide preferably contains a repeating unit represented by the following formula (4-3) as the repeating unit represented by formula (4). In formula (4-3), X １ represents an organic group having 4 or more carbon atoms, and Y １ represents an organic group having 4 or more carbon atoms, and R １ each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. In formula (R-1), L １ represents a2+1-valent linking group, A １ represents a polymerizable group, a2 represents an integer of 1 or more, * represents X in formula (4-3). １ or Y １ represents the binding site with

[0210] -R １ -R １ each independently represents a structure represented by formula (R-1). １ represents a 2+1-valent linking group. １ is preferably a group represented by the following formula (LR-1). In formula (LR-1), L ｘ represents a 2+1-valent linking group, a2 represents an integer of 1 or more, * represents X in formula (4-3). １ or Y １represents a bonding site with A in formula (R-1), １ represents the binding site with L ｘ 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. Preferred embodiments of a2 in formula (LR-1) are the same as the preferred embodiments of a2 in formula (R-1).

[0211] -A １ - A in formula (R-1) １ represents a polymerizable group, and preferred embodiments of the polymerizable group are the same as the preferred embodiments of the polymerizable group in the specific resin described above. １ At least one of the groups is preferably a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloxy group, and more preferably a vinylphenyl group.

[0212] -a2- In formula (R-1), a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. In addition, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0213] -X １ - In formula (4-3), X １ preferably includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. Ｘ２ and R Ｘ３ each independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ may be bonded to form a ring structure.

[0214] In formula (V-2), R Ｘ１are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group has been substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F. In formula (V-3), R Ｘ２ and R Ｘ３ are each preferably independently a hydrogen atom. Ｘ２ and R Ｘ３ When R Ｘ２ and R Ｘ３ The structure formed by bonding is a single bond, —O—, or —CR ２ - is preferred, and -O- or -CR ２ R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.

[0215] X １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1), X １ is preferably a group represented by the following formula (V-1-1): In the following formula, * represents X in formula (4-3). １ represents the bonding sites with the four carbonyl groups to which n1 is bonded, and n1 represents an integer of 0 to 5, and is preferably an integer of 1 to 5. In addition, the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group. In addition, when m in the above formula (4-3) is an integer of 1 to 4, the m hydrogen atoms are bonded to the R １ It is preferred that the substituted group is:

[0216] X １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), X １is preferably a group represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of reducing the amine value in the resin, it is preferably a group represented by formula (V-2-2). Ｘ１ represents a single bond or —O—, and * represents X in formula (4-3). １ represents the bonding site with the four carbonyl groups to which R is bonded. Ｘ１ The definition and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxy groups and hydrocarbon groups. In addition, when m in the above formula (4-3) is an integer of 1 to 4, m hydrogen atoms may be substituted with R in formula (4-3). １ It is preferred that the substituted group is:

[0217] X １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), X １ is preferably a group represented by the following formula (V-3-1) or formula (V-3-2), and from the viewpoint of lowering the dielectric constant, it is preferably a group represented by formula (V-3-2). In the following formulas, * represents X in formula (4-3). １ represents the bonding site with the four carbonyl groups to which R is bonded. Ｘ２ and R Ｘ３ The definition and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxy groups and hydrocarbon groups. In addition, when m in the above formula (4-3) is an integer of 1 to 4, m hydrogen atoms may be substituted with R in formula (4-3). １ It is preferred that the substituted group is:

[0218] X １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), X １ is preferably a group represented by the following formula (V-4-1): In the following formula, * represents X in formula (4-3). １represents the bonding sites with the four carbonyl groups to which n is bonded, and n1 represents an integer of 0 to 5. In addition, the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group. In addition, when m in the above formula (4-3) is an integer of 1 to 4, the m hydrogen atoms are bonded to the R １ It is preferred that the substituted group is:

[0219] Other, X １ is R in the above formula (4). １３２ It may also be a group in which m hydrogen atoms have been removed from a group represented by the following formula: １ It is preferable that the structure does not contain an imide structure. In the present invention, the imide structure is a structure represented by -C(=O)N(-*)C(=O)-. * represents a bonding site with other structures. In addition, X １ In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom. Ｎ —C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ R each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ In the present invention, the amide bond is defined as *-NR Ｎ -C(=O)-*, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ The preferred embodiments of X are as described above. １It is preferable that X does not contain an ester bond in its structure. In the present invention, the ester bond is a bond represented by *--O--C(=O)--*. Among these, X １ It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0220] -Y １ - In formula (4-3), Y １ is preferably a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-4).

[0221] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1), Y １ is preferably a group obtained by removing n hydrogen atoms from a group represented by the following formula (V-1-2): １ represents the bonding site with the two nitrogen atoms to which n is bonded, and n1 represents an integer of 1 to 5. Among the hydrogen atoms in the following structure, n is the R １ n has the same meaning as n in formula (4-3). In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as a hydroxy group or a hydrocarbon group.

[0222] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), １ is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of lowering the dielectric constant, it is preferably a group represented by formula (V-2-4). Ｘ１ represents a single bond or —O—, and * represents Y in formula (4-3). １ represents the bonding site with the two nitrogen atoms to which R is bonded. Ｘ１ The preferred embodiment of is as described above. In the following structure, n hydrogen atoms are R １n has the same meaning as n in formula (4-3). In these structures, the hydrogen atoms may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0223] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), １ is preferably a group represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of lowering the dielectric constant, it is preferably a group represented by formula (V-3-3). In the following formulas, * represents Y in formula (4-3). １ represents the bonding site with the two nitrogen atoms to which R is bonded. Ｘ２ and R Ｘ３ The preferred embodiment of is as described above. In the following structure, n hydrogen atoms are R １ n has the same meaning as n in formula (4-3). In these structures, the hydrogen atoms may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0224] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), １ is preferably a group represented by the following formula (V-4-2): １ represents the bonding site with the two nitrogen atoms to which n is bonded, and n1 represents an integer of 0 to 5. An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. １ n has the same meaning as n in formula (4-3). In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as a hydroxy group or a hydrocarbon group.

[0225] Others, Y １ is R in the above formula (4). １３１ It may also be a group obtained by removing n hydrogen atoms from a group represented by the following formula: １It is preferable that Y does not contain an imide structure in the structure. １ It is preferable that Y does not contain a urethane bond, a urea bond, or an amide bond in the structure. １ It is preferable that Y does not contain an ester bond in the structure. １ It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0226] Among these, X in formula (4-3) １ and Y １ Each of these preferably contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-4).

[0227] In formula (4-3), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (4-3), n is preferably 1 or 2, and more preferably 2.

[0228] The polyimide preferably contains fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0229] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure, specifically, diamine components such as bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0230] In order to improve the storage stability of the resin composition, it is preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0231] -Imidization rate (ring closure rate)- The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the obtained organic film. The upper limit of the imidization rate is not particularly limited, and it is sufficient if it is 100% or less. The imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the absorption peak at 1377 cm －１Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P1 around 1377cm. －１ The peak intensity P2 around the peak intensity P1 is measured. The imidization rate of the polyimide can be calculated using the obtained peak intensities P1 and P2 according to the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[0232] Polyimide is a polymer in which all repeating units are R １３１ and R １３２ The repeating unit may contain the repeating unit represented by the above formula (4) in which the combination of R １３１ and R １３２ The polyimide may contain a repeating unit represented by the formula (4) above, which contains two or more different combinations of repeating units. In addition to the repeating unit represented by the formula (4), the polyimide may contain other types of repeating units. Examples of other types of repeating units include the repeating unit represented by the formula (2) above.

[0233] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid to an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the resulting polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used.

[0234] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but is, for example, 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 polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyimides as one resin are each within the above ranges.

[0235] [Polybenzoxazole Precursor] The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3). In formula (3), R １２１ represents a divalent organic group, and R １２２ represents a tetravalent organic group, R １２３ and R １２４ each independently represents a hydrogen atom or a monovalent organic group.

[0236] In formula (3), R １２３ and R １２４ are R in formula (2), respectively. １１３ In other words, it is preferable that at least one of R is a polymerizable group. １２１represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. １２１ The dicarboxylic acid residue is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types of dicarboxylic acid residues may be used.

[0237] As the dicarboxylic acid residue, dicarboxylic acids containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, with dicarboxylic acid residues containing an aromatic group being more preferred. As the dicarboxylic acid containing an aliphatic group, dicarboxylic acids containing a linear or branched (preferably linear) aliphatic group are preferred, with dicarboxylic acids consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups being more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioctic acid, heneicosanedioctic acid, docosanedioctic acid, tricosanedioctic acid, tetracosanedioctic acid, pentacosanedioctic acid, hexacosanedioctic acid, heptacosanedioctic acid, octacosanedioctic acid, nonacosanedioctic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula:

[0238] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0239] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only a group having an aromatic group and two —COOH groups are more preferred.

[0240] In the formula, A is —CH ２ -, -O-, -S-, -SO ２ -, -CO-, -NHCO-, -C(CF ３ ) ２ - and -C(CH ３ ) ２ - represents a divalent group selected from the group consisting of, and * each independently represents a bonding site to another structure.

[0241] Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0242] In formula (3), R １２２ represents a tetravalent organic group. The tetravalent organic group is R １１５ The same definition and preferred range are also true. １２２is preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino- 3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These groups derived from bisaminophenol derivatives may be used alone or in combination.

[0243] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0244] In the formula, X １ is -O-, -S-, -C(CF ３ ) ２ -, -CH ２ -, -SO ２ R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. １２２ It is also preferable that R is a structure represented by the above formula. １２２is a structure represented by the above formula, any two of the four * and # are R １２２ are bonding sites with the nitrogen atom to which R is bonded, and the other two are bonding sites with the nitrogen atom to which R is bonded in formula (3). １２２ is preferably a bonding site with the oxygen atom to which the two * are bonded, and １２２ is a bonding site with the oxygen atom to which the bond is made, and two #s are R １２２ is a bonding site with the nitrogen atom to which the bond is made, or two * are R １２２ is a bonding site with the nitrogen atom to which the bond is made, and two #s are R １２２ is more preferably a bonding site with the oxygen atom to which the two * are bonded, and １２２ is a bonding site with the oxygen atom to which the bond is made, and two #s are R １２２ is more preferably the bonding site with the nitrogen atom to which is bonded.

[0245] The bisaminophenol derivative is also preferably a compound represented by formula (As).

[0246] In formula (A-s), R １ represents a hydrogen atom, alkylene, substituted alkylene, —O—, —S—, —SO ２ R is -, -CO-, -NHCO-, a single bond, or an organic group selected from the group consisting of the following formula (A-sc): ２ R are either a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. ３ are either a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group or a cyclic alkyl group, and may be the same or different.

[0247] In the organic group selected from the group of formula (A-sc), * indicates that it is bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).

[0248] In formula (As), the ortho position of the phenolic hydroxy group, i.e., R ３It is particularly preferred that the hydroxyl group also has a substituent, as this is thought to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, further enhancing the effect of achieving a high cyclization rate when cured at low temperatures.

[0249] In formula (A-s), R ２ is an alkyl group, and R ３ is preferably an alkyl group, since this can maintain the effects of high transparency to i-rays and a high cyclization rate when cured at low temperatures.

[0250] In formula (A-s), R １ It is more preferred that R is alkylene or substituted alkylene. １ Specific examples of the alkylene and substituted alkylene include linear or branched alkyl groups having 1 to 8 carbon atoms. ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ - is more preferable in that it is possible to obtain a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

[0251] As a method for producing the bisaminophenol derivative represented by Formula (As), reference can be made to, for example, paragraphs

[0085] to

[0094] and Example 1 (paragraphs

[0189] to

[0190] ) of JP2013-256506A, the contents of which are incorporated herein by reference.

[0252] Specific examples of the structure of the bisaminophenol derivative represented by formula (A-s) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Specific examples of the structure of the bisaminophenol derivative represented by formula (A-s) are not limited to these.

[0253] The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of formula (3). The polybenzoxazole precursor preferably contains a diamine residue represented by formula (SL) below as another type of repeating unit, in order to suppress the occurrence of warpage due to ring closure.

[0254] In formula (SL), Z has an a-structure and a b-structure, and R １ｓ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ２ｓ is a hydrocarbon group having 1 to 10 carbon atoms, and R ３ｓ , R ４ｓ , R ５ｓ , R ６ｓ At least one of the above is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, and they may be the same or different. The polymerization of the a-structure and the b-structure may be block polymerization or random polymerization. The mole percentages of the Z moiety are 5 to 95 mole% for the a-structure, 95 to 5 mole% for the b-structure, and a+b is 100 mole%.

[0255] In formula (SL), preferred Z is R in the b structure. ５ｓ and R ６ｓ is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, thereby achieving both the effect of suppressing warpage and the effect of improving solvent solubility.

[0256] When the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Examples of such a tetracarboxylic acid residue include R １１５ Examples include:

[0257] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor be within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as a single resin be within the above-mentioned ranges.

[0258] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group. The polymerizable group is preferably a radically polymerizable group. Alternatively, it may be a compound represented by the following formula (X) having a polarity conversion group such as an acid-decomposable group. In formula (X), R １３３ represents a divalent organic group, and R １３４ represents a tetravalent organic group. In the case where a polarity conversion group such as a polymerizable group or an acid-decomposable group is contained, the polarity conversion group such as the polymerizable group or the acid-decomposable group is １３３ and R １３４ or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2): In formula (X-1), R １３５ and R １３６ At least one of the groups is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and if it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other group has the same meaning as in formula (X). In formula (X-2), R １３７ is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents, and the other groups have the same meanings as in formula (X).

[0259] The polarity conversion group such as the polymerizable group or acid-decomposable group has the same meaning as the polymerizable group described above for the polymerizable group contained in the polyimide precursor.

[0260] R １３３ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. Specific examples include R １２１ Examples include R １２１ is the same as:

[0261] R １３４ represents a tetravalent organic group. The tetravalent organic group is R in formula (3) of the polybenzoxazole precursor. １２２ Examples include R １２２ For example, R １２２ The four bonds of the tetravalent organic group exemplified by R １３４ is the following organic group, the following structure is formed: In the following structure, * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively.

[0262] The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs during oxazolization by heating is reduced, and warpage can be more effectively suppressed. The oxazolization rate can be measured, for example, by the following method. The infrared absorption spectrum of polybenzoxazole is measured, and the absorption peak at 1650 cm, which is derived from the amide structure of the precursor, is detected. －１ Next, the peak intensity Q1 around 1490 cm －１ The polybenzoxazole was heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again. －１ The peak intensity Q2 around 1490 cm －１ The absorption intensity of the aromatic ring observed near the peak intensity Q1 is normalized. Using the normalized values ​​of the peak intensities Q1 and Q2 thus obtained, the oxazolization rate of polybenzoxazole can be calculated based on the following formula: Oxazolization rate (%) = (normalized value of peak intensity Q1 / normalized value of peak intensity Q2) × 100

[0263] Polybenzoxazole is R １３３ and R １３４ The repeating units may contain the same combination of the formula (X) above, and R １３３ and R １３４ The polybenzoxazole may contain repeating units of the formula (X) having two or more different combinations of the repeating units. In addition to the repeating units of the formula (X), the polybenzoxazole may also contain other types of repeating units.

[0264] Polybenzoxazole is, for example, a compound obtained by combining a bisaminophenol derivative and R １３３or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, which is then oxazolized using a known oxazolization reaction method. In the case of a dicarboxylic acid, an activated ester type dicarboxylic acid derivative previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used to increase the reaction yield.

[0265] The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By increasing the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. When two or more polybenzoxazoles are contained, it is preferable that the weight-average molecular weight of at least one polybenzoxazole be within the above range. The number-average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersity of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole is not particularly specified, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the resin composition contains multiple types of polybenzoxazoles as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polybenzoxazole are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polybenzoxazoles as a single resin are each within the above ranges.

[0266] [Polyamideimide Precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). In formula (PAI-2), R １１７ represents a trivalent organic group, R １１１ represents a divalent organic group, A ２ represents an oxygen atom or —NH—, R １１３ represents a hydrogen atom or a monovalent organic group.

[0267] In formula (PAI-2), R １１７ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms or may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0268] Also, R １１７ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Two of the three carboxy groups in the tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and are used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0269] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0270] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are bonded with a single bond, —O—, —CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -SO ２ These compounds may be compounds in which two carboxy groups are anhydride (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0271] In formula (PAI-2), R １１１ , A ２ , R １１３ are R in the above formula (2), １１１ , A ２ , R １１３ The same applies to the preferred embodiments.

[0272] The polyamideimide precursor may further contain other repeating units, such as the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1):

[0273] In formula (PAI-1), R １１６ represents a divalent organic group, R １１１ represents a divalent organic group. １１６is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２ Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms or may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0274] Also, R １１６is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound. The carboxy groups in the dicarboxylic acid dihalide compound may be halogenated, but are preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of optionally halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamideimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0275] Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0276] Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, and sebacic acid. Examples of the nonanedioic acid include hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosaneedioic acid, heneicosaneedioic acid, docosaneedioic acid, tricosaneedioic acid, tetracosaneedioic acid, pentacosaneedioic acid, hexacosaneedioic acid, heptacosaneedioic acid, octacosaneedioic acid, nonacosaneedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

[0277] In formula (PAI-1), R １１１ is R in the above formula (2) １１１ The same applies to the preferred embodiments.

[0278] The polyamideimide precursor preferably has fluorine atoms in its structure, and the fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0279] Furthermore, for the purpose of improving adhesion to a substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as a diamine component.

[0280] One embodiment of the polyamideimide precursor of the present invention includes a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), and a repeating unit represented by formula (2). The total content of these repeating units is preferably 50 mol% or more of all repeating units, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, but is 100 mol% or less. All repeating units in the polyamideimide precursor excluding the terminal repeating units may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Another embodiment of the polyamideimide precursor of the present invention includes a repeating unit represented by formula (PAI-2) and a repeating unit represented by formula (PAI-1). The total content of the repeating units is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol% of all repeating units. The upper limit of the total content is not particularly limited, but is 100 mol% or less. All repeating units in the polyamideimide precursor excluding the terminal repeating units may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0281] The weight-average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly specified, but is, for example, 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 polyamideimide precursors as the specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide precursor be within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity, calculated by treating the plurality of types of polyamideimide precursors as one resin, are each within the above-mentioned ranges.

[0282] [Polyamideimide] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide, or may be a polyamideimide soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 0.1 g or more. From the viewpoint of pattern formability, a polyamideimide that dissolves at 0.5 g or more is preferred, and a polyamideimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamideimide is preferably a polyamideimide having multiple amide bonds and multiple imide structures in the main chain.

[0283] -Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyamideimide contains a fluorine atom. The fluorine atom is, for example, R in the repeating unit represented by formula (PAI-3) described later. １１７, or R １１１ and R in the repeating unit represented by formula (PAI-3) described below is preferably included. １１７ , or R １１１ The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more and 20% by mass or less.

[0284] - Ethylenically unsaturated bond - From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond. The polyamideimide may have the ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable that the ethylenically unsaturated bond be in a side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is formed by the R １１７ , or R １１１ and R in the repeating unit represented by formula (PAI-3) described below is preferably included. １１７ , or R １１１ It is more preferable that the group having an ethylenically unsaturated bond is contained as a group having an ethylenically unsaturated bond in the following formula: Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.

[0285] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0286] -Polymerizable Group Other Than Ethylenically Unsaturated Bond- The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond. Examples of the polymerizable group other than an ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable group other than an ethylenically unsaturated bond in the polyimide described above. Examples of the polymerizable group other than an ethylenically unsaturated bond include, for example, R １１１The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0287] - Polarity conversion group - The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide is represented by R １１３ and R １１４ The acid-decomposable group is the same as that described above, and the preferred embodiments are also the same.

[0288] -Acid Value- When the polyamideimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. Furthermore, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. Furthermore, when the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (e.g., "solvent development"), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. Furthermore, examples of acid groups contained in the polyamideimide include the same groups as the acid groups in the polyimides described above, and preferred embodiments are also the same.

[0289] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyamideimide preferably has a phenolic hydroxy group. The polyamideimide may have the phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group can be, for example, R in the repeating unit represented by formula (PAI-3) described below. １１７ , or R １１１The amount of phenolic hydroxy groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0290] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). In formula (PAI-3), R １１１ and R １１７ are R in formula (PAI-2), respectively. １１１ and R １１７ In the case where the polymerizable group is present, the polymerizable group is R １１１ and R １１７ or may be located at the end of the polyamideimide.

[0291] In order to improve the storage stability of the resin composition, it is preferable to cap the main chain ends of the polyamideimide with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. Preferred embodiments of the terminal capping agent are the same as those of the terminal capping agent for the polyimide described above.

[0292] -Imidization rate (ring closure rate)- The imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoints of the film strength, insulating properties, etc. of the resulting organic film. The upper limit of the imidization rate is not particularly limited, and it is sufficient if it is 100% or less. The imidization rate is measured by the same method as the ring closure rate of polyimide described above.

[0293] Polyamideimide is R １１１ and R １１７ The repeating unit may contain the repeating unit represented by the formula (PAI-3) in which the combination of R １１１ and R １１７The polyamideimide may contain a repeating unit represented by formula (PAI-3) above, which contains two or more different combinations of repeating units. In addition to the repeating unit represented by formula (PAI-3), the polyamideimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (PAI-1) or formula (PAI-2) above.

[0294] Polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or by terminating the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyamideimide precursor to introduce a partial imide structure.

[0295] The weight-average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By increasing the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. The number-average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamideimide 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 molecular weight dispersity of the polyamideimide, 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 polyamideimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyamideimides as a single resin are each within the above-mentioned ranges.

[0296] [Method for Producing Polyimide Precursors, etc.] Polyimide precursors, etc., can be obtained by, for example, reacting a tetracarboxylic dianhydride with a diamine at low temperature, reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine with the diamine. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine with the diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0297] -End-capping agent- In order to further improve storage stability during the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of the end-capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and in terms of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of suitable end-capping agents include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple end-capping agents may be reacted to introduce multiple different end groups. Furthermore, when capping the amino groups at the resin ends, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred examples of the capping agent for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0298] -Solid Precipitation- The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is poured into a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a polyimide precursor or the like. To improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0299] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0300] It is also preferable that the resin composition of the present invention contains at least two kinds of resins. Specifically, the resin composition of the present invention may contain a total of two or more kinds of the specific resin and other resins described later, or may contain two or more kinds of specific resins, but it is preferable that the resin composition of the present invention contains two or more kinds of specific resins. When the resin composition of the present invention contains two or more kinds of specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R １１５ ) preferably contains two or more different polyimide precursors.

[0301] <Other Resins> The resin composition of the present invention may contain the specific resin described above and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of at least 100 mol / g) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0302] When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. The content of the other resin in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0303] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0304] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0305] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0306] 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.

[0307] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a 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. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0308] 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 WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0309] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0310] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0311] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0312] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0313] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0314] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0315] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U") is also preferred. In the present invention, the urea bond is a radical crosslinking agent having at least one selected from the group consisting of *-NR Ｎ —C(═O)—NR Ｎ- is a bond represented by *, and R Ｎ each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. When the resin composition contains crosslinking agent U, chemical resistance, resolution, etc. may be improved. The mechanism by which the above effect is achieved is unclear; however, it is thought that, for example, when curing by heating, a portion of crosslinking agent U is thermally decomposed to generate amines, etc., which then promote the cyclization of precursors of cyclized resins such as polyimide precursors. Examples of crosslinking agent U include the compounds described in paragraphs 0133 to 0143 of WO 2023 / 190064. The contents of this document are incorporated herein by reference.

[0316] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. 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, 1,6-hexyl ... Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of 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. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0317] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on 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.

[0318] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0319] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. It is preferably a compound having multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator. A compound having multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base is more preferred. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator during the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0320] The resin composition of the present invention preferably contains a photosensitizer, such as a polymerization initiator or a photoacid generator.

[0321] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0322] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0323] Any known compound can be used as the 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 oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details of these compounds, please refer to paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

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

[0324] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0325] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0326] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and 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).

[0327] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0328] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0329] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0330] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0331] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0332]

[0333] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0334] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0335] In addition, compounds described in paragraphs 0113 to 0117 of JP-A No. 2023-058585 can also be used as the photopolymerization initiator, the disclosure of which is incorporated herein by reference.

[0336] When the resin composition contains a photopolymerization initiator, the content thereof 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. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0337] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0338] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0339] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0340] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0341] When 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, relative to 100 parts by mass of the total solid content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0342] In another preferred embodiment of the present invention, the resin composition of the present invention contains two or more polymerization initiators. Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0343] By including a photopolymerization initiator and a thermal polymerization initiator described below, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by a heating step described below, which may improve performance such as chemical resistance. When a photopolymerization initiator and a thermal polymerization initiator described below are included, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0344] Inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, the content ratio of the photoacid generator relative to the total content of the photopolymerization initiator and the photoacid generator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %.

[0345] [Thermal Polymerization Initiator] Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0346] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0347] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. The resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are contained, the total amount is preferably in the above range.

[0348] [Photoacid Generator] The resin composition of the present invention preferably contains a photoacid generator. The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. The irradiated light preferably has a wavelength of 300 nm to 450 nm, more preferably 330 nm to 420 nm. The photoacid generator is preferably capable of generating an acid upon photosensitization, either alone or in combination with a sensitizer. Preferred examples of the acid that can be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogenated peroxides, and sulfonamides.

[0349] Examples of photoacid generators include quinone diazide compounds, oxime sulfonate compounds, organic halogen compounds, organic borate compounds, disulfone compounds, onium salt compounds, etc. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, etc., oxime esters are preferred.

[0350] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent amino compound via sulfonamide, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxy polyamino compound. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds need to be substituted with quinone diazide, but it is preferred that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By incorporating such quinone diazide compounds, it is possible to obtain a resin composition that is photosensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.

[0351] Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOC. P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-P CHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriM L-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP -PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Asahi Yu Examples of suitable phenolic resins include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resins.

[0352] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0353] Specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0354] Among these, it is preferable that the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group, which can provide higher sensitivity to i-line exposure and higher resolution.

[0355] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, a contrast between exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

[0356] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also simply referred to as "oxime sulfonate compound"). There are no particular limitations on the oxime sulfonate compound as long as it has an oxime sulfonate group, and examples thereof include the compounds described in paragraphs 0208 to 0209 of WO 2023 / 112573, the contents of which are incorporated herein by reference.

[0357] Examples of organic halogenated compounds include compounds described in paragraphs 0042 to 0043 of JP 2015-087409 A, the contents of which are incorporated herein by reference.

[0358] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination with multiple types. In the case of a combination of multiple types, it is preferable that the total amount thereof is within the above range. It is also preferable to use it in combination with a sensitizer to impart photosensitivity to a desired light source.

[0359] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0140 to 0143 of WO 2024 / 150700. The above descriptions are incorporated herein by reference.

[0360] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0144 to 0146 of WO 2024 / 150700.

[0361] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0362] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0363] The base generator is preferably an amine in which the amino group is protected with a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

[0364] 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, diethanolamine diamine, 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-butanolbis(3-aminopropyl)ethanol ter, 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 a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

[0365] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the 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 generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0366] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0367] 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, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ...alkyloxypropionate, ethyl 3-alkyloxypropionate, 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3- Preferred examples thereof include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (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), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0368] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0369] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0370] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0371] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0372] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0373] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0374] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0375] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0376] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0377] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass %, more preferably an amount such that the total solids concentration is 5 to 75 mass %, even more preferably an amount such that the total solids concentration is 10 to 70 mass %, and even more preferably an amount such that the total solids concentration is 20 to 70 mass %. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0378] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0379] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, 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 JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the formula below, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0380]

[0381] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of suitable silane coupling agents 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-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups may also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1): In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. Ｓ１is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred. R Ｓ２ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Such oligomer-type compounds can be commercially available products, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0382] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0383] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0384] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0385] <Migration Inhibitor> The resin composition of the present invention 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, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0386] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0387] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0388] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of this specification are incorporated herein by reference.

[0389] Specific examples of the migration inhibitor include the following compounds.

[0390]

[0391] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0392] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0393] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0394] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like, the contents of which are incorporated herein by reference.

[0395] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solid content of the resin composition.

[0396] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0397] <Light absorber> The resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength is reduced by exposure. Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.

[0398] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0399] <Other Additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101 to 0104, 0107 to 0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0400] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0401] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared can be further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with little thickness unevenness.

[0402] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy gr...

Claims

1. A bonded structure formed by bonding a first member having a first base material, a first insulating pattern arranged on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern arranged on the second base material, and a second conductive pattern present between the second insulating patterns, wherein the angle formed between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the bonded structure is greater than 90° and not greater than 110°.

2. A bonded body obtained by bonding a first member having a first base material, a first insulating pattern arranged on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern arranged on the second base material, and a second conductive pattern present between the second insulating patterns, wherein the angle formed between the bottom surface of the first conductive pattern and the side surface of the first conductive pattern in the first member before bonding is greater than 90° and not greater than 110°.

3. The bonded body according to claim 1 or 2, wherein the difference between the maximum and minimum distances from the surface of the first substrate of the first component to the surface of the first conductive pattern on the side opposite the first substrate in a direction perpendicular to the surface of the first substrate of the first component before bonding is 500 nm or less.

4. The bonded body according to claim 1 or 2, wherein the first conductive pattern in the first member before bonding is a pillar pattern, and the diameter of the first conductive pattern is 0.1 μm or more and 10 μm or less.

5. The bonded body according to claim 1 or 2, wherein the first conductive pattern in the first member before bonding contains at least one metal selected from the group consisting of Cu, Sn, Ni, Ag, Bi, In, Sb and Ti.

6. The joined body according to claim 1 or 2, wherein the surface of the first conductive pattern in the first member before joining contains at least Sn.

7. The bonded body according to claim 1 or 2, wherein the surface of the first conductive pattern in the first member before bonding contains at least Cu.

8. The bonded body according to claim 1 or 2, wherein the indentation elastic modulus of the first insulating pattern in the first member before bonding is 6.0 GPa or less.

9. The bonded structure according to claim 1 or 2, wherein the first insulating pattern in the first member before bonding contains polyimide.

10. The conjugate according to claim 9, wherein the cyclization rate of said polyimide is 70% or more.

11. The bonded body according to claim 1 or 2, wherein the first insulating pattern in the first member before bonding contains an ionic compound.

12. The bonded body according to claim 1 or 2, wherein the second conductive pattern in the second member before bonding is a pillar pattern or a pad pattern, and the diameter or side length of the second conductive pattern is 0.1 μm or more and 10 μm or less.

13. The joined body according to claim 1 or 2, wherein the second conductive pattern in the second member before joining contains at least one of Cu, Sn, Ni, Ag, Bi, In, Sb, and Ti.

14. The joined body according to claim 1 or 2, wherein the surface of the second conductive pattern in the second member before joining contains at least Sn.

15. The bonded body according to claim 1 or 2, wherein the surface of the second conductive pattern in the second member before bonding contains at least Cu.

16. The bonded body according to claim 1 or 2, wherein the indentation elastic modulus of the second insulating pattern in the second member before bonding is 6.0 GPa or less.

17. The bonded structure according to claim 1 or 2, wherein the second insulating pattern in the second member before bonding contains polyimide.

18. The conjugate according to claim 17, wherein the cyclization rate of the polyimide is 70% or more.

19. The bonded body according to claim 1 or 2, wherein the second insulating pattern in the second member before bonding contains an ionic compound.

20. The bonded body according to claim 1 or 2, wherein the second insulating pattern in the second member before bonding includes an inorganic insulating film.

21. The second insulating pattern in the second member before the bonding is made of SiN, SiO ２ 3. The joined body according to claim 1, wherein the joined body contains at least one of SiCN and SiCN.

22. The bonded structure according to claim 1 or 2, wherein at least one of the first substrate and the second substrate includes a redistribution layer.

23. A method for manufacturing a bonded body that bonds a first member having a first base material, a first insulating pattern disposed on the first base material, and a first conductive pattern present between the first insulating patterns, and a second member having a second base material, a second insulating pattern disposed on the second base material, and a second conductive pattern present between the second insulating patterns, the method comprising: a conductive layer forming step of forming a conductive layer on the first insulating pattern and in regions between the first insulating patterns of the first base material on which the first insulating pattern is formed, to obtain member A; a polishing step of polishing member A to obtain a first member having the first conductive pattern and the first insulating pattern exposed on its surface; and a bonding step of bonding the first member and a second member to obtain a member, wherein the angle formed between at least the bottom surface of the conductive pattern of the first member and the side surface of the conductive pattern is greater than 90° and not greater than 110°.

24. A method for producing a junction body according to claim 23, further comprising, prior to the conductive layer forming step, a film forming step including applying a first insulating pattern forming composition onto the first substrate to form a film, wherein the first insulating pattern forming composition contains at least one compound selected from the group consisting of a photoradical polymerization initiator and a photoacid generator.

25. The method for producing a bonded body according to claim 24, wherein the i-line transmittance of a 3 μm thick film formed by heating the first insulating pattern-forming composition at 100° C. for 3 minutes is 5% or more.

26. A method for forming an insulating pattern comprising, after the film-forming step, a drying step of drying the film, an exposure step of exposing the dried film to light, and a development step of developing the exposed film using a developer, wherein the first insulating pattern-forming composition is applied to a silicon wafer and heated at 100°C for 180 seconds, and then the first insulating pattern-forming composition is applied to a silicon wafer at a dose of 100 mJ / cm ２ 26. The method for producing a joined body according to claim 25, wherein the film is irradiated with i-rays at an exposure dose of 1000 nm and heated at 110°C for 3 minutes, and the swelling rate of the film in the developer is 15% by volume or less.

27. The method for producing a bonded body according to claim 26, further comprising, after the film-forming step, a heating step of heating the film at two or more heating temperatures.

28. The method for producing a bonded body according to any one of claims 23 to 27, wherein at least one of the first substrate and the second substrate includes a rewiring layer.

29. A photosensitive resin composition used in forming the first insulating pattern in the manufacturing method according to any one of claims 23 to 27.

30. The photosensitive resin composition according to claim 29, comprising a polyimide or a polyimide precursor.

31. A semiconductor device comprising the junction of claim 1 or 2.

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