Layered body and layered body manufacturing method

Abstract

A layered body and a layered body manufacturing method, said layered body comprising: a first rewiring layer that has a first insulating pattern and a first conductive pattern present between the pattern of the first insulating pattern, and includes a first via structure as the first conductive pattern; and a second rewiring layer that has a second insulating pattern and a second conductive pattern present between the pattern of the second insulating pattern, and includes a second via structure as the second conductive pattern, wherein in a projection plane in the thickness direction of the first via structure, an upper surface of the first via structure and at least one section of a bottom surface of the second via structure are overlapping, the upper surface of the first via structure and the bottom surface of the second via structure in the overlapping region are electrically connected by a conductive section, and the flatness of a second via structure-side surface of the conductive section is 2 μm or less.

Description

Laminate and method for manufacturing laminate

[0001] The present invention relates to a laminate and a method for manufacturing the laminate.

[0002] Today, semiconductor packages are used in mobile phones, tablet devices, and various other electronic devices. A semiconductor package is a case that protects components such as delicate semiconductor chips and electronic circuits from the external environment and mounts them on a substrate such as a printed wiring board. The semiconductor package functions to transmit signals generated by the components to other devices and transmit signals from other devices to the components. Mobile phones, tablet devices, and other electronic devices are becoming increasingly smaller, lighter, and more multifunctional. To meet these needs, semiconductor packages are also required to be even smaller, more highly integrated, and more densely packed. Advances in wiring technology, such as those using rewiring layers, are desired.

[0003] For example, Patent Document 1 describes a semiconductor package including: a semiconductor die having conductive terminals and a protective layer covering sidewalls of the conductive terminals; a first redistribution circuit structure disposed on the semiconductor die and electrically coupled to the semiconductor die; and a surface modification film disposed between the first redistribution circuit structure and the semiconductor die and having a plurality of openings that expose edges of the conductive terminals, the surface modification film having a bonding interface between the surface modification film and the protective layer formed of Si—O—C bonds. Patent Document 2 describes a semiconductor package including a first redistribution layer, a second redistribution layer, a first semiconductor die, and a second semiconductor die, the first redistribution layer including a first surface and a second surface opposite the first surface, the second redistribution layer being disposed on the first surface of the first redistribution layer, the first semiconductor die being disposed on the first redistribution layer and the second redistribution layer and being electrically connected to the first redistribution layer and the second redistribution layer, and the second semiconductor die being disposed on the second redistribution layer and being electrically connected to the second redistribution layer.

[0004] US Patent Application Publication No. 2022 / 0336310 US Patent Application Publication No. 2021 / 0035908

[0005] Here, laminates used in semiconductor packages and the like that use rewiring layers are required to have excellent reliability, where reliability refers to the property of continuously exhibiting required performance such as insulation and adhesiveness.

[0006] An object of the present invention is to provide a highly reliable laminate and a method for producing the laminate.

[0007] Representative embodiments of the present invention are described below: <1> A laminate comprising: a first redistribution layer having a first insulating pattern and a first conductive pattern present between the first insulating patterns, the first redistribution layer including a first via structure as the first conductive pattern; and a second redistribution layer having a second insulating pattern and a second conductive pattern present between the second insulating patterns, the second redistribution layer including a second via structure as the second conductive pattern, wherein an upper surface of the first via structure overlaps with at least a part of a bottom surface of the second via structure in a projection plane in a depth direction of the first via structure, the upper surface of the first via structure and the bottom surface of the second via structure in the overlapping region are connected by a conductive portion, and the flatness of the surface of the conductive portion facing the second via structure is 2 μm or less. <2> The laminate according to <1>, further comprising an encapsulating layer including at least one semiconductor die and an encapsulant, wherein the first redistribution layer is formed on the semiconductor die, and the first conductive pattern is electrically connected to the semiconductor die. <3> The laminate according to <1> or <2>, further comprising: a third redistribution layer having a third insulating pattern and a third conductive pattern present between the third insulating patterns, and including a third via structure as the third conductive pattern, wherein an upper surface of the second via structure overlaps with at least a part of a bottom surface of the third via structure in a projection plane in a via depth direction, the upper surface of the second via structure and the bottom surface of the third via structure in the overlapping region are connected by a second conductive portion, and the flatness of the surface of the second conductive portion facing the third via structure is 2 μm or less. <4> The laminate according to any one of <1> to <3>, wherein the angle formed between the bottom surface of the first insulating pattern and the side surface of the first insulating pattern in the first via structure is 80° or more and less than 90°. <5> The laminate according to any one of <1> to <4>, wherein the conductive portion includes a line and space pattern, and the minimum width of the conductive portion in the line and space pattern is 0.1 to 20 μm. <6> The laminate according to any one of <1> to <5>, wherein the first redistribution layer has a thickness of 0.1 to 20 μm.<7> The laminate according to any one of <1> to <6>, wherein the first conductive pattern has a barrier layer. <8> The laminate according to any one of <1> to <7>, wherein the first insulating pattern has a breaking elongation of 40% or more. <9> The laminate according to any one of <1> to <8>, wherein the first insulating pattern has a glass transition temperature of 230°C or more. <10> The laminate according to any one of <1> to <9>, wherein the first insulating pattern has a Young's modulus of 2.5 GPa or more. <11> A method for manufacturing a laminate, comprising: a first redistribution layer forming step of forming a first redistribution layer having a first insulating pattern and a first conductive pattern existing between the first insulating patterns, the first redistribution layer including a first via structure as the first conductive pattern; a conductive portion forming step of forming a conductive portion in contact with the first via structure; and a second redistribution layer forming step of forming a second redistribution layer having a second insulating pattern and a second conductive pattern existing between the second insulating patterns, the second redistribution layer including a second via structure in contact with the conductive portion as the second conductive pattern, wherein an upper surface of the first via structure and at least a part of a bottom surface of the second via structure overlap in a projection plane in a via depth direction, and a flatness of a surface of the conductive portion facing the second via structure is 2 μm or less. <12> A method for manufacturing a laminate according to <11>, further comprising a polishing step of polishing a surface of the first redistribution layer between the first redistribution layer forming step and the conductive portion forming step. <13> The method for producing a laminate according to <11> or <12>, wherein the first redistribution layer forming step includes a film forming step of applying a first insulating pattern forming composition on a substrate to form a film. <14> The method for producing a laminate according to <13>, wherein the substrate includes an encapsulating layer containing at least one semiconductor die and an encapsulant, and in the film forming step, the first insulating pattern forming composition is applied on the semiconductor die to form an electrically connected first conductive pattern and the semiconductor die. <15> The method for producing a laminate according to <13> or <14>, wherein the first insulating pattern forming composition contains at least one resin selected from the group consisting of polyimide and polyimide precursors.<16> A method for producing a laminate according to any one of <13> to <15>, comprising the steps of applying the first insulating pattern-forming composition to a substrate to form a coating film, drying, exposing, and developing the coating film to form a precursor pattern, and heating the precursor pattern to obtain a first insulating pattern, wherein the rate of change in film thickness of the first insulating pattern relative to the precursor pattern is less than 10%. <17> A method for producing a laminate according to any one of <13> to <16>, wherein the resin comprises a polyimide having an imidization rate of 50% or more. <18> A method for producing a laminate according to any one of <13> to <17>, wherein a coating film coated with the composition has a Young's modulus of 2.5 GPa or more after heating at 230°C for 3 hours. <19> A method for producing a laminate according to any one of <13> to <18>, wherein the resin comprises a polyimide precursor having an imidization rate of less than 50%. <20> The method for producing a laminate according to any one of <13> to <19>, wherein the composition contains a transmittance adjuster. <21> The method for producing a laminate according to <20>, wherein the transmittance adjuster contains at least one compound selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[0008] According to the present invention, a highly reliable laminate and a method for producing the laminate are provided.

[0009] Fig. 3 is a schematic cross-sectional view showing a specific example of a conductive connection portion. Fig. 4 is a schematic cross-sectional view showing an example of a laminate of the present invention. Fig. 5 is a schematic projection view of the laminate shown in Fig. 2 observed in the depth direction of the first via structure from the surface on which the connection pad is formed. Fig. 6 is a schematic cross-sectional view showing another example of a laminate of the present invention. Fig. 7 is a schematic cross-sectional view showing an example of a method for manufacturing a laminate of the present invention (continuation of Fig. 5). Fig. 8 is a schematic cross-sectional view showing an example of a method for manufacturing a laminate of the present invention (continuation of Fig. 6). Fig. 9 is a schematic cross-sectional view of a laminate formed in this example.

[0010] 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-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, for example, due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is above or below the reference layer among the multiple layers being considered. In other words, 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 (sealing layer) is referred to as "above." Alternatively, if a composition layer is present, the direction from the substrate to the composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, 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 herein, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment. In this specification, the shape of the pattern is arbitrary and is not limited to only regular shapes.

[0011] (Laminate) The laminate of the present invention (hereinafter also simply referred to as "laminate") comprises: a first redistribution layer having a first insulating pattern and a first conductive pattern present between the first insulating patterns, and including a first via structure as the first conductive pattern; and a second redistribution layer having a second insulating pattern and a second conductive pattern present between the second insulating patterns, and including a second via structure as the second conductive pattern, wherein an upper surface of the first via structure and at least a part of a bottom surface of the second via structure overlap on a projection plane in a depth direction of the first via structure, the upper surface of the first via structure and the bottom surface of the second via structure in the overlapping region are connected by a conductive portion, and the flatness of the surface of the conductive portion on the second via structure side is 2 μm or less.

[0012] The laminate of the present invention has excellent reliability. The mechanism by which the above effect is achieved is unknown, but is speculated as follows. To improve pattern density, it is required to vertically stack the via portions in the rewiring layer so that they overlap on the projection surface (forming a stacked via structure). However, in conventional rewiring layers, distortion occurs during the formation of the via structure, reducing the flatness of the conductive pattern, making it difficult to stack the second via structure. Furthermore, since the second via structure is also formed with distortion, stress concentration occurs within the layer. For example, when used for a long period of time, or particularly when heated and cooled repeatedly (e.g., TCT cycles), cracks are likely to occur in the insulating pattern near the via structure, resulting in poor reliability. However, in the present invention, the flatness of the surface of the conductive pattern facing the second via structure is 2 μm or less, making it difficult to generate distortion in the formed second via structure, allowing the second via structure to be easily stacked, and the occurrence of the above-mentioned cracks is suppressed, thereby improving reliability.

[0013] The laminate of the present invention will be described in detail below.

[0014] <First Redistribution Layer> The laminate of the present invention includes a first redistribution layer having a first insulating pattern and a first conductive pattern present between the first insulating patterns, and including a first via structure as the first conductive pattern.

[0015] [First insulating pattern] The volume resistivity of the first insulating pattern at 25°C is not particularly limited, but is preferably 1×10 ８ It is preferable that the resistance is Ω cm or more, and 1×10 １０ More preferably, it is 1×10 Ω cm or more. １２ The upper limit is not particularly limited, but is, for example, 1×10 １８ It is preferably Ω·cm or less.

[0016] The first insulating pattern preferably contains a resin, more preferably a polyimide, and is preferably a cured product of a first insulating pattern-forming composition described below.

[0017] The breaking elongation of the first insulating pattern is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. There are no particular limitations on the upper limit of the breaking elongation, and it is preferably, for example, 100% or less. The breaking elongation is measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min in an environment of 25°C and 65% RH (relative humidity) according to the method described in JIS-K6251. The breaking elongation can be adjusted by the structure and content of the resin, polymerizable compound, etc. contained in the first insulating pattern-forming composition described below.

[0018] The glass transition temperature of the first insulating pattern is preferably 220°C or higher, more preferably 230°C or higher, and even more preferably 240°C or higher. There are no particular restrictions on the upper limit of the glass transition temperature, but it can be set to, for example, 350°C or lower. The glass transition temperature can be measured by changing the temperature conditions of the first insulating pattern in the following order (1) to (4), creating a differential scanning calorimetry curve, and measuring the temperature at the intersection of a line extending the low-temperature baseline of the differential scanning calorimetry curve toward the high-temperature side and a tangent drawn at the point where the gradient of the curve in the stepwise change portion of the glass transition is maximum. (1) Heat from 25°C to 300°C at a rate of 10°C / min. (2) Cool from 300°C to 25°C. (3) Heat from 25°C to 500°C at a rate of 10°C / min. (4) Cool from 500°C to 25°C. The glass transition temperature can be adjusted by the structure and content of the specific resin, polymerizable compound, etc. contained in the first insulating pattern-forming composition, which will be described later.

[0019] The Young's modulus of the first insulating pattern is preferably 2.5 GPa or more. The Young's modulus is more preferably 2.7 GPa or more, and even more preferably 3.0 GPa or more. There is no particular upper limit to the Young's modulus, but it is preferably, for example, 10.0 GPa or less. The Young's modulus is measured by a tensile test at 25°C. Specifically, the Young's modulus is measured in accordance with JIS-K7161-1 (2014) using a DMA850 (TA Instruments) at a crosshead speed of 5 mm / min, at 25°C, and in an environment of 65% RH (relative humidity).

[0020] The coefficient of thermal expansion (CTE) of the first insulating pattern is preferably 10 to 70 ppm / K, more preferably 15 to 65 ppm / K, and even more preferably 20 to 60 ppm / K. The coefficient of thermal expansion of the first insulating pattern is measured by the following method. The elongation (displacement) of the first insulating pattern is measured while changing the temperature using a thermomechanical analyzer / thermal expansion coefficient measuring device, Discovery TMA, manufactured by TA Instruments Japan Co., Ltd. The heating and cooling conditions during evaluation are as follows (1) to (4): (1) Raise the temperature from room temperature to 130°C at a heating rate of 5°C / min. (2) Lower the temperature from 130°C to 10°C at a heating rate of 5°C / min. (3) Raise the temperature from 10°C to 220°C at a heating rate of 5°C / min. (4) Allow to cool naturally to room temperature. The elongation (displacement) of the sample is measured during the temperature increase and decrease processes of (1) to (4) above, and the thermal expansion coefficient is calculated by dividing the longitudinal elongation (displacement) of the sample at 25°C and 125°C in process (3) by the temperature.

[0021] [First Conductive Pattern] The volume resistivity of the first conductive pattern at 25°C is not particularly limited, but is preferably 1×10 －５ It is preferably Ω cm or less, and 1×10 －６ It is more preferable that the resistance is Ω cm or less, and 1×10 －７ The lower limit is not particularly limited, but for example, it is 1×10 －１１ It is preferably Ω·cm or more.

[0022] The material constituting the first conductive pattern is preferably copper. The metal is not particularly limited and any existing metal species can be used, but examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing at least one of these metals. Copper, aluminum, or alloys containing at least one of these metals are preferred, copper or an alloy containing copper is more preferred, and copper is even more preferred.

[0023] The first conductive pattern preferably has a barrier layer at least in part. The first conductive pattern preferably has a barrier layer between the first insulating pattern and at least one of the connection portions between the first conductive pattern and the conductive portion. By having a barrier layer, it is possible to prevent migration of the material (metal, etc.) constituting the conductive pattern to other components such as the first insulating pattern or the sealing layer.

[0024] The material constituting the barrier layer is not particularly limited, but examples thereof include tungsten, titanium, and an alloy containing at least one of these metals. Alternatively, the barrier layer may be formed using a metal having a lower ionization tendency than the material constituting the first conductive pattern.

[0025] [Via Structure] The via structure is a structure for connecting two adjacent layers to the first redistribution layer, and is preferably a structure having a substantially cylindrical shape, a substantially polygonal prism shape, or the like. The diameter of the via structure (in the case of a polygonal prism shape, the circle-equivalent diameter) is not particularly limited, but is preferably 1 to 20 μm, and more preferably 1 to 10 μm. The via structure is formed by the first conductive pattern. Furthermore, other layers, such as a seed layer for forming the first conductive pattern, may be further formed within the via structure.

[0026] In the first via structure, the angle formed between the bottom surface of the first insulating pattern and the side surface of the first insulating pattern (hereinafter also referred to as the "taper angle") is preferably 80° or more and less than 90°, more preferably 80 to 88°, and even more preferably 80 to 85°. Here, when there is distortion in the side surface of the via structure, the taper angle is defined as the angle formed between the bottom surface of the first insulating pattern and a straight line connecting an end point of the bottom surface of the first insulating pattern and an end point of the exposed portion of the insulating pattern on the top surface side of the first insulating pattern. In this specification, the bottom surface refers to the surface closer to the sealing layer, and the top surface refers to the surface farther from the sealing layer.

[0027] The taper angle is determined by cleaving the laminate at a plane including the center of the via structure, polishing the cross section with a milling device ArBlade 5000 (manufactured by Hitachi, Ltd.), obtaining an SEM image with an FE-SEM SU-4800 (manufactured by Hitachi, Ltd.), and measuring the angle between the bottom surface of the first insulating pattern and the side surface of the first insulating pattern. The taper angle can be adjusted by the structure and content of the resin, polymerizable compound, etc. contained in the first insulating pattern-forming composition described below, the numerical aperture, exposure dose, exposure illuminance of the exposure light in forming the first insulating pattern, the type of developer used during development, and the like.

[0028] The thickness of the first redistribution layer is not particularly limited, but is preferably 0.1 to 20 μm. The upper limit of the thickness is not particularly limited, but is preferably 15 μm or less, and more preferably 10 μm or less.

[0029] <Second Redistribution Layer> Preferred aspects of the second insulating pattern, second conductive pattern, and second via structure in the second redistribution layer are the same as those in the first redistribution layer. The second redistribution layer is preferably formed on the first redistribution layer. Other preferred aspects of the second redistribution layer are the same as those in the first redistribution layer.

[0030] The thickness of the second redistribution layer is not particularly limited, but is preferably 0.1 to 20 μm. The upper limit of the thickness is not particularly limited, but is preferably 15 μm or less, and more preferably 10 μm or less.

[0031] <Positional Relationship of Via Structures> In a projection plane in the depth direction of the first via structure, the top surface of the first via structure and at least a portion of the bottom surface of the second via structure overlap. Here, the top surface of the first via structure refers to the surface of the first via structure facing the second redistribution layer, and the bottom surface of the first via structure refers to the surface of the first via structure opposite the second redistribution layer. Furthermore, the bottom surface of the second via structure refers to the surface of the second via structure facing the first redistribution layer, and the top surface of the second via structure refers to the surface of the second via structure opposite the first redistribution layer. The depth direction of the via structure refers to the direction connecting the center of the top surface of the via structure to the center of the bottom surface of the via structure.

[0032] Here, it is preferable that the depth direction of the first via structure and the depth direction of the second via structure are approximately the same. Of the bottom surface of the second via structure, it is preferable that 90 area % or more overlaps with the top surface of the first via structure, more preferably 95 area % or more overlaps with the top surface of the first via structure, and even more preferably 99 area % or more overlaps with the top surface of the first via structure. Here, an embodiment in which 100 area % of the bottom surface of the second via structure overlaps with the top surface of the first via structure is also one of the preferred embodiments of the present invention.

[0033] When either or both of the first redistribution layer and the second redistribution layer have multiple via structures, at least one combination of them may be such that, in a projection plane in the depth direction of the first via structure, the top surface of the first via structure overlaps with at least a portion of the bottom surface of the second via structure.

[0034] <Conductive portion> The laminate of the present invention includes a conductive portion. The top surface of the first via structure and the bottom surface of the second via structure are connected by the conductive portion in the overlapping region. The conductive portion may further be connected to at least one of another first conductive pattern and another second conductive pattern.

[0035] The conductive portion is preferably formed as a layer containing a conductive portion and an insulating pattern (hereinafter also referred to as a "conductive portion-containing layer"). The conductive portion-containing layer preferably contacts the first redistribution layer on one side and the second redistribution layer on another side. A preferred embodiment of the insulating pattern is the same as the preferred embodiment of the second insulating pattern described above.

[0036] The material for forming the conductive portion is preferably a metal. The metal is not particularly limited and any existing metal species can be used, but examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing at least one of these metals. Copper, aluminum, or alloys containing at least one of these metals are preferred, copper or an alloy containing copper is more preferred, and copper is even more preferred.

[0037] The layer including the conductive portion and the insulating pattern preferably includes a line-and-space pattern. The line-and-space pattern is, for example, included as a line-and-space pattern in which the conductive portion is the line portion and the insulating pattern is the space portion. When the conductive portion includes a line-and-space pattern, the minimum width of the conductive portion (the width of the narrowest line portion among the conductive portions) is preferably 0.1 to 20 μm. The upper limit of the width is more preferably 15 μm or less, and even more preferably 10 μm or less. The lower limit of the width is not particularly limited, but can be, for example, 0.1 μm or more. When the conductive portion includes a line-and-space pattern, the width of the narrowest space portion among the space portions is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. The lower limit of the width is not particularly limited, but can be, for example, 0.1 μm or more.

[0038] The flatness of the surface of the conductive portion on the side of the second via structure is 2 μm or less. Here, flatness is defined as the difference between the maximum and minimum distances from the substrate to the surface of the conductive portion. The flatness is preferably 1.5 μm or less, and more preferably 1.0 μm or less. The flatness is measured by the method described in the Examples below.

[0039] The thickness of the conductive portion is not particularly limited, but is preferably 0.1 to 20 μm. The upper limit of the thickness is not particularly limited, but is preferably 15 μm or less, and more preferably 10 μm or less.

[0040] <Third Redistribution Layer> The laminate of the present invention also preferably includes a third redistribution layer. The third redistribution layer includes a third insulating pattern and a third conductive pattern present between the third insulating patterns, and includes a third via structure as the third conductive pattern. Preferred aspects of the third insulating pattern, the third conductive pattern, and the third via structure in the third redistribution layer are the same as those in the first redistribution layer. The third redistribution layer is preferably formed on the second redistribution layer. Other preferred aspects of the third redistribution layer are the same as those in the first redistribution layer.

[0041] The thickness of the third redistribution layer is not particularly limited, but is preferably 0.1 to 20 μm. The upper limit of the thickness is not particularly limited, but is preferably 15 μm or less, and more preferably 10 μm or less.

[0042] In a projection plane in the depth direction of the via, the upper surface of the second via structure and at least a portion of the bottom surface of the third via structure overlap, and the upper surface of the second via structure and the bottom surface of the third via structure in the overlapping region are connected by a second conductive portion, and it is preferable that the flatness of the surface of the second conductive portion on the third via structure side is 2 μm or less. Here, preferred aspects of the second conductive portion are the same as the preferred aspects of the conductive portion described above. That is, it is preferable that the second conductive portion is formed as a layer including the second conductive portion and an insulating pattern (hereinafter also referred to as a "second conductive portion-containing layer"). It is preferable that the second conductive portion-containing layer contacts the second redistribution layer on one side and the third redistribution layer on another side.

[0043] The thickness of the second conductive portion is not particularly limited, but is preferably 0.1 to 20 μm. The upper limit of the thickness is not particularly limited, but is preferably 15 μm or less, and more preferably 10 μm or less.

[0044] Preferably, 50 area % or more of the bottom surface of the third via structure overlaps with the top surface of the second via structure, more preferably 80 area % or more of the bottom surface of the third via structure overlaps with the top surface of the second via structure, and even more preferably 90 area % or more of the bottom surface of the third via structure overlaps with the top surface of the second via structure. Here, an embodiment in which 100 area % of the bottom surface of the third via structure overlaps with the top surface of the second via structure is also one of the preferred embodiments of the present invention.

[0045] If either or both of the second redistribution layer and the third redistribution layer have multiple via structures, at least one combination of them may be such that, in a projection plane in the depth direction of the second via structure, the top surface of the second via structure overlaps with at least a portion of the bottom surface of the third via structure.

[0046] <Another Rewiring Layer> The laminate of the present invention may further include another rewiring layer. The other rewiring layer includes another insulating pattern and another conductive pattern present between the other insulating patterns, and includes another via structure as the other conductive pattern. Preferred aspects of the other insulating pattern, other conductive pattern, and other via structure in the other rewiring layer are the same as those in the first rewiring layer. The other rewiring layer is preferably formed on a third rewiring layer. Here, it is also a preferred aspect that the other rewiring layer, the other conductive portion, and the other rewiring layer are stacked in this order. In the present invention, a structure including a first rewiring layer and a second rewiring layer, optionally including a third rewiring layer, and optionally further including another rewiring layer is also referred to as a rewiring stacked structure. It is also preferred that the rewiring stacked structure includes a first rewiring layer, a conductive portion, a second rewiring layer, a second conductive portion, a third rewiring layer, a third conductive portion, and another rewiring layer, in this order. The rewiring stack structure preferably includes a total of 3 to 20 rewiring layers, more preferably 4 to 10. Other preferred aspects of the other rewiring layers are the same as the preferred aspects of the first rewiring layer.

[0047] <Connection Pad> The laminate of the present invention may further include a connection pad in the outermost layer of the rewiring laminate structure. The connection pad is not particularly limited, and examples thereof include connection pads formed from the same metal as the first pattern. Other connection pads known in the art can also be used without particular limitation.

[0048] <Substrate> The laminate of the present invention preferably includes a substrate. In the laminate of the present invention, the substrate preferably contacts the side of the first rewiring layer opposite the side where the second rewiring layer is present. The substrate is not particularly limited, and may include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin-On-Glass), TFT (Thin Film Transistor) array substrates, and plasma display panel (PDP) electrode plates, but is not particularly limited thereto. These substrates may have a surface layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS), a sealant (epoxy molding compound: EMC), or the like. The substrate may be in the form of a wafer or a panel. In the present invention, a semiconductor production 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. Preferably, the electronic circuit is electrically connected to the first conductive pattern. The substrate may further include a conductive member for connecting to another member on a surface different from the surface connected to the first conductive pattern.

[0049] [Sealing Layer] The laminate of the present invention preferably further comprises a sealing layer containing at least one semiconductor die as a base material and a sealing material. Specifically, the laminate of the present invention preferably further comprises a sealing layer containing at least one semiconductor die and a sealing material, the first redistribution layer being formed on the semiconductor die, and the first conductive pattern being electrically connected to the semiconductor die.

[0050] In one preferred embodiment of the present invention, the encapsulation layer includes an encapsulant and at least one semiconductor die, and the semiconductor die is embedded in the encapsulant.

[0051] -Sealant- The sealant is not particularly limited and any known sealant can be used, but it is preferably one obtained by curing a curable composition (curable adhesive). Examples of the curable composition include various curable compositions, such as photocurable compositions (e.g., ultraviolet curable), reactive curable compositions (e.g., anaerobic curable or moisture curable), and thermosetting compositions. Two-component mixture compositions and adhesive sheets may also be used. These curable compositions are preferably curable resin compositions, and examples of resins that can be used include epoxy resins, silicone resins, acrylic resins, phenolic resins, polyimide resins, imide resins, PVC (polyvinyl chloride) resins, PVB (polyvinyl butyral) resins, and EVA (ethylene vinyl acetate) resins. The curable resin composition may further contain other components in addition to the resin, such as fillers, polymerization initiators, curing agents, and desiccants. These components may be any conventionally known components in this field, without any particular limitations.

[0052] [Semiconductor Die] In the present invention, a semiconductor die refers to a chip incorporating a circuit, and refers to a die that exhibits functions such as memory and logic. The semiconductor die is preferably a semiconductor chip. The semiconductor die can be obtained, for example, by forming a circuit pattern on a substrate such as silicon and then dividing it into individual pieces. The semiconductor die is not particularly limited, but examples include memory ICs, logic ICs, ASICs, and those further integrated into an integrated circuit.

[0053] The number of semiconductor dies encapsulated in the encapsulation layer is not particularly limited, and may be one or more. Here, a preferred embodiment of the present invention is one in which the encapsulation layer contains two or more semiconductor dies, and the circuits of two or more of the two or more semiconductor dies are connected to the first redistribution layer. The size of the semiconductor die is not particularly limited, and examples thereof include those with a side length of 100 μm to 10 cm.

[0054] The semiconductor die may include a conductive member that connects to the circuitry of the semiconductor die. Examples of the conductive member include a conductive pad. Examples of materials for the conductive member include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing at least one of these metals. Copper, aluminum, or an alloy containing at least one of these metals is preferred, copper or an alloy containing copper is more preferred, and copper is even more preferred.

[0055] Preferably, the circuit of the semiconductor die or the conductive member is exposed on one surface of the encapsulation layer, and preferably, the circuit of the semiconductor die or the conductive member is exposed on one surface of the encapsulation layer, and neither the circuit of the semiconductor die nor the conductive member is exposed on the other surface of the encapsulation layer. Also, preferably, the exposed circuit or the conductive member connected to the circuit is connected to the first redistribution layer.

[0056] - Conductive Through Portion - The sealing layer preferably further includes a conductive through portion that electrically connects one surface of the sealing layer to the other surface of the sealing layer. Such a conductive through portion is preferably included as, for example, a conductive through via that penetrates the sealing layer. The conductive through portion connects, for example, the first redistribution layer to another member.

[0057] The thickness of the sealing layer is not particularly limited and may be determined taking into consideration the thickness of the semiconductor die, etc., but is preferably 1 μm to 500 μm, and more preferably 10 μm to 200 μm, for example.

[0058] <Other Semiconductor Die> The laminate of the present invention preferably further includes one or more semiconductor dies that are not included in the encapsulation layer and are electrically connected to the first redistribution layer. Preferred aspects of the other semiconductor dies are the same as the preferred aspects of the semiconductor dies included in the encapsulation layer, except that they are not encapsulated in the encapsulation layer. The other semiconductor dies are preferably disposed, for example, on the opposite side of the substrate from the first redistribution layer and electrically connected to the first redistribution layer.

[0059] When the laminate of the present invention includes other semiconductor dies, the number of other semiconductor dies may be one or more, preferably one to ten, and more preferably one to four. Also, a preferred embodiment of the present invention includes two or more other semiconductor dies. In the above embodiment, the number of other semiconductor dies is more preferably three or more, even more preferably five or more, and particularly preferably ten or more. In such an embodiment, when two or more semiconductor dies are included, the semiconductor dies may be the same or different.

[0060] <Conductive Connection Portion> The laminate of the present invention may further include a conductive connection portion on a surface of the rewiring laminate structure different from the surface that contacts the substrate. The conductive connection portion is preferably either a substantially spherical depression, a substantially columnar shape, or a bonding pad structure with an average diameter of 5 μm or less. The laminate of the present invention may also include a barrier layer between the rewiring laminate structure and the conductive connection portion.

[0061] When the conductive connection portion has a substantially spherical indentation shape, the conductive connection portion is preferably a solder ball, a ball grid array (BGA) ball, or a C4 bump. Fig. 1( a) is a schematic cross-sectional view of a conductive connection portion having a substantially spherical indentation shape. In Fig. 1( a), the conductive connection portion 102 is connected to a conductive pattern 108 in the outermost layer of the redistribution layered structure via a conductive pad 104, and the conductive pattern 108 is formed between insulating patterns 106 in the outermost layer of the redistribution layered structure. A barrier layer may be formed between the conductive pad 104 and the conductive pattern 108.

[0062] When the conductive connection portion has a substantially spherical depression shape, the material constituting the conductive connection portion is not particularly limited, but is preferably Sn, Pb, Ag, Cu, Ni, Bi, or an alloy containing any of these. When the conductive connection portion has a substantially spherical depression shape, the height of the conductive connection portion is preferably 50 μm or less, more preferably 20 to 50 μm, and even more preferably 20 to 40 μm.

[0063] When the conductive connection portion is substantially columnar, it is preferable that the conductive connection portion be a pillar having a solder member on the upper portion. FIG. 1( b) is a schematic cross-sectional view of a case where the conductive connection portion is substantially columnar. In FIG. 1( b), the conductive connection portion 102 is a member consisting of a solder member 110 and a pillar 112. In FIG. 1( b), the solder member 110 is depicted as being hemispherical, but this shape is not particularly limited, and the solder member 110 may be cylindrical or have a flat top. In FIG. 1( b), the conductive connection portion 102 is connected to a conductive pattern 108, and the conductive pattern 108 is formed between insulating patterns 106.

[0064] When the conductive connection portion is substantially columnar, the material constituting the pillar is not particularly limited, but is preferably Sn, Pb, Ag, Cu, Ni, Bi, or an alloy containing any of these, and more preferably Cu. When a solder member is included, the material constituting the solder member is not particularly limited, but is preferably Sn, Pb, Ni, Bi, or an alloy containing any of these. When the conductive connection portion is substantially columnar, the height of the conductive connection portion is preferably 20 μm or less, more preferably 10 to 20 μm, and even more preferably 10 to 15 μm.

[0065] When the conductive connection portion has a bonding pad structure with an average diameter of 5 μm or less, the conductive connection portion is preferably formed so that its height is aligned with the insulating pattern and the conductive connection portion and the insulating member are substantially flat. Figure 1(c) is a schematic cross-sectional view of a conductive connection portion having a bonding pad structure with an average diameter of 5 μm or less. In Figure 1(c), the conductive connection portion 102 is connected to a conductive pattern 108, and the conductive pattern 108 is formed between insulating patterns 106.

[0066] When the conductive connection portion is a bonding pad structure having an average diameter of 5 μm or less, the material constituting the bonding pad structure is not particularly limited, but is preferably Sn, Pb, Ag, Cu, Ni, Bi, or an alloy containing any of these, and more preferably Cu. When the conductive connection portion is a bonding pad structure having an average diameter of 5 μm or less, the average diameter is 5 μm or less, preferably 1 to 5 μm, and more preferably 2 to 5 μm. The average diameter is the average diameter of the upper surface of the bonding pad structure. When the upper surface of the bonding pad structure is not circular, the average diameter refers to the average value of the circle-equivalent diameter.

[0067] <Substrate> The laminate of the present invention may have a substrate connected to the conductive connection portion. The material of the substrate is not particularly limited, and may include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe; paper; SOG (Spin-on-Glass); TFT (Thin Film Transistor) array substrates; and plasma display panel (PDP) electrode plates, among others. These substrates 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 the form of a wafer or a panel. In the present invention, semiconductor production substrates are particularly preferred, and silicon substrates (silicon wafers) are more preferred. The substrate may have an electronic circuit region containing an electronic circuit. The electronic circuit may also have elements such as semiconductors. Preferably, the electronic circuit is electrically connected to the first conductive pattern. The substrate may further include a conductive member for connecting to another member on a surface different from the surface connected to the first conductive pattern.

[0068] <Another Redistribution Layer Structure> The laminate of the present invention may further include another redistribution layer structure. The other redistribution layer structure is preferably disposed on the opposite side of the substrate from the first redistribution layer and is present between the substrate and the other semiconductor die. The other redistribution layer structure includes an insulating pattern and a conductive pattern present between the insulating patterns. Known insulating patterns and conductive patterns in the other redistribution layer structure can be used without particular limitation, but they can be formed using the same materials as the first insulating pattern and the first conductive pattern in the first redistribution layer. The other redistribution layer structure preferably includes a total of 3 to 20 redistribution layers, more preferably 4 to 10 redistribution layers.

[0069] <Specific Examples of Laminates> Specific examples of laminates of the present invention will be described below with reference to the drawings, but the present invention is not limited thereto. In each drawing, already explained reference numerals may be omitted. FIG. 2 is a schematic cross-sectional view showing an example of a laminate of the present invention. In the following drawings, the interface between the conductive pattern and the conductive portion, and the interface between the insulating patterns are depicted for convenience, but in reality, these interfaces may not always be clear. Furthermore, there may be cases where no interface exists at all, such as when multiple layers of insulating patterns are formed simultaneously. In FIG. 2 , a laminate 10 has a first redistribution layer including a first conductive pattern 14 formed between first insulating patterns 12, and the first redistribution layer includes a first via structure 16. Also in FIG. 2 , a layer including an insulating pattern 18 and a conductive pattern 20 is formed on the first redistribution layer. In FIG. 2 , a first redistribution layer including a second conductive pattern 26 formed between second insulating patterns 24 (conductive portion-containing layer) is formed on the layer including the insulating pattern 18 and the conductive pattern 20, and the second redistribution layer includes a second via structure 28. 2, a connection pad 30 is formed on the side of the second redistribution layer opposite the first redistribution layer. The first via structure 16 and the second via structure 28 are connected by a conductive portion 22. Here, in a projection plane in the depth direction of the first via structure 16, the top surface of the first via structure and at least a portion of the bottom surface of the second via structure 28 overlap. FIG. 3 is a schematic projection diagram of the laminate 10 depicted in FIG. 2, observed in the depth direction of the first via structure 16 from the surface on which the connection pad 30 is formed. In FIG. 3, the bottom surface 34 (dashed line) of the second via structure 28 is formed inside the top surface 32 (dotted line) of the first via structure 16, and 100% of the area of ​​the bottom surface 34 of the second via structure overlaps the top surface 32 of the first via structure.

[0070] 4 is a schematic cross-sectional view showing another example of the laminate of the present invention. In FIG. 4 , a rewiring laminate structure is formed by stacking, in order, a first rewiring layer 42 including a first via structure 16, a conductive portion-containing layer 44 including a conductive portion 22, a second rewiring layer 46 including a second via structure 28, a second conductive portion-containing layer 50 including a second conductive portion 48, a third rewiring layer 54 including a third via structure 52, a third conductive portion-containing layer 58 including a third conductive portion 56, and another rewiring layer 62 including another conductive pattern 60, on an encapsulation layer 40 in which a semiconductor die 36 is embedded in an encapsulation material 38 as a base material. Here, in a projection plane in the depth direction of the first via structure, the bottom surface of the second via structure 28 overlaps with the top surface of the first via structure 16. Furthermore, in a projection plane in the depth direction of the second via structure, the bottom surface of the third via structure 52 preferably overlaps with the top surface of the second via structure 28. The flatness of the surface of the conductive portion facing the second via structure is 2 μm or less. The flatness of the surface of the second conductive portion facing the via structure is preferably 2 μm or less. The flatness of the surface of the third conductive portion facing the via structure is preferably 2 μm or less.

[0071] A connection pad 30 is formed on the side of this redistribution layered structure opposite the first redistribution layer 42. A conductive connection portion 64 is also formed on the connection pad 30. In FIG. 4, the conductive connection portion 64 is depicted as having a generally spherical indentation, but as described above, it may have other shapes, such as a generally columnar shape or a bonding pad. The redistribution layered structure is connected to a substrate 66 via the conductive connection portion 64, and an electrode 68 and another connection portion 70 are further formed on the side of the substrate 66 opposite the redistribution layered structure.

[0072] Another redistribution layer structure 72 is formed on the side of the encapsulation layer 40 opposite the redistribution layer structure. The other redistribution layer structure includes a conductive pattern and an insulating pattern, and another connection pad 74 is formed on the surface opposite the encapsulation layer. Preferably, the conductive through via 37 and the other connection pad 74 are electrically connected by the conductive pattern. The other connection pad 74 is also connected to another semiconductor die 78 via a connection portion 76. Because the conductive through via 37 is formed in the encapsulation layer 40, the first redistribution layer 42 is connected to the other semiconductor die 78 via the conductive through via 37, the other connection pad 74, and the connection portion 76.

[0073] (Method for manufacturing laminate) A method for manufacturing a laminate of the present invention includes: a first redistribution layer forming step of forming a first redistribution layer having a first insulating pattern and a first conductive pattern present between the first insulating patterns, and including a first via structure as the first conductive pattern; a conductive portion forming step of forming a conductive portion in contact with the first via structure; and a second redistribution layer forming step of forming a second redistribution layer having a second insulating pattern and a second conductive pattern present between the second insulating patterns, and including a second via structure in contact with the conductive portion as the second conductive pattern, wherein an upper surface of the first via structure and at least a part of a bottom surface of the second via structure overlap on a projection plane in a depth direction of the via, and the flatness of the surface of the conductive portion on the second via structure side is 2 μm or less.

[0074] According to the method for producing a laminate of the present invention, the above-mentioned laminate of the present invention can be obtained, that is, a laminate with excellent reliability can be obtained.

[0075] <First rewiring layer forming step> The method for manufacturing a laminate of the present invention includes a first rewiring layer forming step of forming a first rewiring layer having a first insulating pattern and a first conductive pattern present between the first insulating patterns, and including a first via structure as the first conductive pattern.

[0076] The preferred embodiments of the first insulating pattern, the preferred embodiments of the first conductive pattern, and the preferred embodiments of the via structure are as described above.

[0077] The first redistribution layer formation step preferably includes applying a first insulating pattern-forming composition to a substrate to form a film (film formation step). The first redistribution layer formation step more preferably includes the film formation step, an exposure step of selectively exposing the film formed by the film formation step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern. The first redistribution layer formation step particularly preferably includes the film formation step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step. Details of each step will be described below. Details of the first insulating pattern-forming composition (hereinafter also simply referred to as "composition") will be described later.

[0078] <Film Forming Step> The first rewiring layer forming step preferably includes a film forming step of applying a composition onto a substrate to form a film.

[0079] The substrate may be the same as the substrate in the laminate of the present invention described above. In particular, the substrate preferably includes a sealing layer containing at least one semiconductor die and a sealing material, and the first insulating pattern-forming composition is applied to the semiconductor die in the film-forming step to electrically connect the first conductive pattern and the semiconductor die. The sealing layer containing at least one semiconductor die and a sealing material is formed, for example, by the sealing layer-forming step described below.

[0080] Coating is preferred as a means for applying the 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, and inkjet coating are preferred, and from the viewpoints of film thickness uniformity and productivity, spin coating and slit coating are more preferred. A film of the desired thickness can be obtained by adjusting the solids concentration of the composition and coating conditions depending on the application method. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film previously formed by applying it to a temporary support using the above-mentioned application method is transferred to the substrate. Regarding the transfer method, the fabrication 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 the composition is applied to improve the wettability of the substrate, and then the composition is applied.

[0081] <Drying Step> After the film formation step (layer formation step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the first redistribution layer formation step may include a drying step of drying the film formed in the film formation step. The drying step is preferably carried out after the film formation 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.

[0082] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The first redistribution layer formation step may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, 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 harden the film, but for example, it may be 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.

[0083] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0084] 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 at least a part of the film is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0085] <Post-Exposure Baking Step> The film may be subjected to a heating step (post-exposure baking step) after exposure. That is, the first redistribution layer formation step may include a post-exposure baking step in which the film exposed in the exposure step is heated. The post-exposure baking step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure baking 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 baking 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.

[0086] <Developing Step> The film after exposure may be subjected to a developing step in which the film is developed using a developer to form a pattern. That is, the first redistribution layer forming step may include a developing 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 developing step is called negative development, and development in which the exposed portions of the film are removed in the developing step is called positive development.

[0087] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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-diamino Examples of the alkyl ester include pentane, 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.

[0095] 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.

[0096] 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.

[0097] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0098] [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.

[0099] The development time is preferably 3 seconds to 10 minutes, more preferably 5 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.

[0100] 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.

[0101] [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.

[0102] 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.

[0103] 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 cyclohexanone or PGMEA.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0108] [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.

[0109] 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.

[0110] 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.

[0111] 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, the basic compound, and the base generator are the same as the preferred aspects of the organic solvent, 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.

[0112] 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.

[0113] <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 first rewiring layer formation step may include a heating step in which the pattern obtained by the development step is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. In addition, crosslinking of unreacted crosslinkable groups in the specific resin or in 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.

[0114] 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.

[0115] 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.

[0116] 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 step of heating up to the maximum heating temperature. For example, when a composition 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 that is 30 to 200°C lower than the boiling point of the solvent contained in the composition.

[0117] 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.

[0118] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0119] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 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 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably from 1 to 5°C / min.

[0120] 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.

[0121] <Post-development exposure step> The pattern obtained by 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 by the development step is exposed to light, instead of or in addition to the heating step. That is, the first redistribution layer formation step may include a post-development exposure step in which the pattern obtained by the development step is exposed to light. The first redistribution layer formation step 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.

[0122] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. The pattern obtained by the developing step corresponds to the first insulating pattern, and the metal layer formed by the metal layer forming step corresponds to the first conductive pattern. That is, the first redistribution layer forming step preferably includes a metal layer forming step in which a metal layer is formed on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0123] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0124] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations thereof. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using copper sulfate or copper cyanide plating solutions. Furthermore, the metal layer formation step preferably includes forming a barrier layer on the formed metal layer after the metal layer is formed. The barrier layer can be formed by any conventionally known method without any particular limitation.

[0125] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0126] <Surface Activation Treatment Step> The first redistribution layer formation step preferably includes a surface activation treatment step in which at least a portion of the metal layer and the composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the composition layer after exposure, or may be performed on at least a portion of both the metal layer and the composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the composition layer (film) formed on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the composition layer, adhesion with the metal layer or resin layer formed on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the composition layer is cured, it is less susceptible to damage caused by the surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this document are incorporated herein by reference.

[0127] <Conductive Portion Forming Step> The laminate manufacturing method of the present invention further includes a conductive portion forming step of forming a conductive portion in contact with the first via structure. The conductive portion forming step preferably includes forming a resist layer, filling the spaces between the resist with metal, and then peeling off the resist layer. The metal filling can be performed using the same method as in the metal layer forming step described above. The resist layer can be formed and peeled off using a known method. Here, the first rewiring layer forming step may include a resist layer forming step before the metal layer forming step, and a resist layer peeling step after the metal layer is formed, thereby simultaneously forming the first conductive pattern and the conductive portion. However, in order to perform the polishing step described below, it is also a preferred embodiment of the present invention that the first conductive pattern and the conductive portion are formed separately.

[0128] <Polishing Step> The first redistribution layer forming step may further include a polishing step of polishing the surface of the first redistribution layer between the first redistribution layer forming step and the conductive portion forming step. Examples of the polishing method include chemical mechanical polishing (CMP) and physical polishing, but are not limited thereto, and any known method can be used without particular limitation.

[0129] <Second Redistribution Layer Forming Step> The method for manufacturing a laminate of the present invention includes a second redistribution layer forming step of forming a second redistribution layer having a second insulating pattern and a second conductive pattern present between the second insulating patterns, and including a second via structure as the second conductive pattern in contact with the conductive portion. The second redistribution layer forming step can be performed by a method similar to that of the first redistribution layer forming step. Preferred aspects of the second redistribution layer obtained by the second redistribution layer forming step are the same as the preferred aspects of the second redistribution layer in the laminate of the present invention described above.

[0130] <Third Redistribution Layer Forming Step, Other Redistribution Layer Forming Step> The method for manufacturing a laminate of the present invention may include a third redistribution layer forming step of forming a third redistribution layer having a third insulating pattern and a third conductive pattern present between the third insulating patterns, and including a third via structure as the third conductive pattern. The method for manufacturing a laminate of the present invention may also include an other redistribution layer forming step having another insulating pattern and another conductive pattern present between the other insulating patterns. These steps can be performed in the same manner as the first redistribution layer forming step. Preferred aspects of the third redistribution layer obtained by the third redistribution layer forming step are the same as the preferred aspects of the third redistribution layer in the laminate of the present invention described above. Preferred aspects of the other redistribution layer obtained by the other redistribution layer forming step are the same as the preferred aspects of the other redistribution layer in the laminate of the present invention described above.

[0131] <Sealing layer forming step> The method for manufacturing a laminate of the present invention may include a sealing layer forming step. The sealing layer forming step provides a sealing layer comprising an encapsulant and a semiconductor die, with the circuit of the semiconductor die exposed on one side and the circuit of the above-mentioned member not exposed on the other side. The sealing layer forming step can be performed, for example, by placing the semiconductor die on a carrier wafer (temporary support), applying the above-mentioned curable composition so as to embed the semiconductor die, and curing the composition. A known temporary adhesive layer may also be formed on the carrier wafer. The application and curing of these layers can be performed with reference to known methods. Preferred embodiments of the curable composition and semiconductor die are as described above.

[0132] In addition, in the encapsulation layer formation step, the surface of the encapsulant may be polished after curing. Examples of such polishing include, but are not limited to, chemical mechanical polishing (CMP) and physical polishing. For example, by polishing the encapsulant after curing on the side of the semiconductor die having the circuit, the circuit of the semiconductor die can be exposed on the surface of the encapsulation layer. Alternatively, any method known in the art can be used for the encapsulation layer formation step, as long as it forms an encapsulation layer. Alternatively, the encapsulation layer formation step may not involve polishing, and the circuit may be exposed from the encapsulation layer by simply not encapsulating the side of the semiconductor die on which the circuit is located.

[0133] A preferred embodiment of the sealing layer obtained by the sealing layer forming step is the same as the preferred embodiment of the sealing layer in the laminate of the present invention described above, except that the conductive portion may not be formed in the sealing layer forming step, and the conductive portion may be formed after at least one of the first rewiring layer forming step and the other rewiring laminate structure forming step, as described below.

[0134] <Passivation Layer Forming Step> The method for manufacturing a laminate of the present invention may further include a passivation layer forming step of forming a passivation layer after the encapsulation layer forming step. The passivation layer forming step is preferably performed after the encapsulation layer forming step and before the first rewiring layer forming step. The passivation layer is formed by coating the circuit surface of the semiconductor die with a passivation film. The formation of the passivation layer may suppress the influence of the outside air, the adhesion of dust, and contamination by water or metals on the semiconductor die. The material of the passivation layer is not particularly limited, but may be SiO ２ , SiN, etc. In addition, resins such as polyimide may also be used. The coating method is not particularly limited and known methods can be used. For example, when it is desired to coat with SiN, CVD (chemical vapor deposition) or the like can be used.

[0135] <Connection Pad Forming Step> The method for producing a laminate of the present invention may further include a connection pad forming step. Preferred embodiments of the connection pad to be formed are as described above. For the connection pad forming step, a method known in the art can be used without particular limitation, and examples include a method in which a resist layer is formed as needed, followed by forming a connection pad by plating or the like, and then peeling off the resist layer.

[0136] Here, one preferred embodiment of the present invention is one in which the first redistribution layer forming step includes a step of applying the first insulating pattern forming composition to a substrate to form a coating film, a step of drying, exposing, and developing the coating film to form a precursor pattern, and a step of heating the precursor pattern to obtain a first insulating pattern, and the film thickness change rate of the first insulating pattern relative to the precursor pattern is less than 10%. Here, the coating, drying, exposing, developing, and heating are performed by the above-mentioned film forming step, drying step, exposing step, developing step, and heating step. The film thickness change rate is calculated as (film thickness of precursor pattern - film thickness of first insulating pattern) / film thickness of precursor pattern x 100. The film thickness change rate is preferably 8% or less, more preferably 5% or less. Furthermore, the lower limit of the film thickness change rate is not particularly limited, and may be 0% or more.

[0137] <Step of Forming Another Redistribution Layer Structure> The method for manufacturing a laminate of the present invention may include a step of forming another redistribution layer structure on the surface of the substrate opposite to the surface on which the first redistribution layer is formed, the another redistribution layer structure including an insulating pattern and a conductive pattern present between the insulating patterns. The another redistribution layer structure is formed by the step of forming another redistribution layer structure. Preferred aspects of the another redistribution layer structure are the same as the preferred aspects of the another redistribution layer structure in the laminate of the present invention described above.

[0138] The other redistribution layer structure forming step can be carried out in the same manner as the above-mentioned first redistribution layer forming step, second redistribution layer forming step, etc., except that it is formed on the surface of the encapsulant where the circuit is not exposed. In the other redistribution layer structure forming step, the other redistribution layer structure can also be formed using the first insulating pattern forming composition in the same manner as in the formation of the redistribution layer structure. Here, the first insulating pattern forming composition used to form the redistribution layer structure and the composition used to form the other redistribution layer structure may have the same composition or different compositions.

[0139] <Carrier Wafer Bonding Step, Carrier Wafer Peeling Step> The method for manufacturing a laminate of the present invention can include a carrier wafer bonding step of bonding a carrier wafer to a laminate being manufactured, and a carrier wafer peeling step of peeling off the bonded carrier wafer. For example, in the sealing layer forming step, a carrier wafer is bonded to a semiconductor die to form a sealing layer on the carrier wafer, and a rewiring stack structure is formed on the substrate by the first rewiring layer forming step and the second rewiring layer forming step. In order to form another rewiring stack structure, the carrier wafer can be peeled off from the sealing layer, and if necessary, a new carrier wafer can be bonded to the surface of the rewiring stack structure, thereby inverting the side on which the carrier wafer is located. The carrier wafer peeling step and the carrier wafer bonding step can be performed by known methods. Furthermore, known carrier wafers can be used without any particular limitations.

[0140] <Conductive Portion Forming Step> The method for manufacturing a laminate of the present invention may further include a conductive portion forming step of forming the aforementioned through-hole conductive portion. The conductive portion forming step may be performed, for example, before the first rewiring layer forming step and the other rewiring laminate structure forming step, or after at least one of the first rewiring layer forming step and the other rewiring laminate structure forming step. The conductive portion forming step is performed, for example, by forming holes in the sealing layer using a laser or the like and filling the holes with a conductor by plating or the like. The holes may be through holes or blind holes. Furthermore, in forming the holes, residues of the sealing layer and the like generated during processing may be removed by a known desmearing process or the like. The conductive portion forming step may be performed by any method known in the art without particular limitation.

[0141] <Conductive Connection Forming Step> The method for producing a laminate of the present invention may further include a conductive connection forming step of forming a conductive connection on a surface of the rewiring laminate structure other than the surface that contacts the substrate. Preferred aspects of the conductive connection are the same as the preferred aspects of the conductive connection of the laminate of the present invention. As a method for forming the conductive connection, any method known in the art can be used without particular limitation.

[0142] <Step of Bonding Another Semiconductor Die> The method for manufacturing a laminate of the present invention may further include a step of bonding another semiconductor die to a surface of the other rewiring laminate structure other than the surface that contacts the substrate. Preferred aspects of the other semiconductor die are the same as the preferred aspects of the other semiconductor die of the laminate of the present invention. When bonding the other semiconductor die, at least one of heating and pressure may be applied. As a method for bonding the other semiconductor die, any method known in the art can be used without particular limitation.

[0143] <Substrate Bonding Step> The method for manufacturing a laminate of the present invention may further include a step of bonding a substrate to a surface of the redistribution layered structure other than the surface in contact with the sealing layer. The substrate is preferably connected to the redistribution layered structure via the above-mentioned conductive connection part. Preferred aspects of the substrate are the same as the preferred aspects of the substrate of the laminate of the present invention. At least one of heating and pressure may be applied during bonding of the substrates. As a method for bonding the substrates, any method known in the art can be used without particular limitation.

[0144] <Other Steps> The method for producing a laminate of the present invention may further include other steps, such as washing the members after each step as necessary.

[0145] <Specific Example of a Method for Producing a Laminate> Specific examples of the method for producing a laminate of the present invention will be described below with reference to the drawings, but the present invention is not limited thereto. In each drawing, already-described reference numerals may be omitted. FIG. 5 is a schematic cross-sectional view illustrating an example of a method for producing a laminate of the present invention. FIG. 5( a) is a schematic cross-sectional view illustrating a state in which an encapsulating layer 40, in which a semiconductor die 36 is encapsulated with an encapsulant 38, is bonded to a carrier wafer 80. The encapsulating layer 40 is obtained by forming an encapsulant by a method such as applying a curable composition to the carrier wafer 80 and the semiconductor die 36 shown in FIG. 5( a) and curing the composition. Furthermore, conductive through vias 37 are formed in the encapsulating layer 40 by a conductive portion formation step. Prior to the subsequent first redistribution layer formation step, the surface of the encapsulating layer 40 may be polished by the above-described method to expose the circuitry of the semiconductor die 36, or the above-described passivation layer formation step may be performed on the surface of the semiconductor die 36 having the circuitry.

[0146] 5B is a schematic cross-sectional view showing a state in which a second carrier wafer 82 is bonded and the carrier wafer 80 is peeled off after the other redistribution layer structure 72 is formed by the other redistribution layer structure forming process. The other redistribution layer structure is formed by performing the other redistribution layer structure forming process on the surface of the encapsulation layer 40 shown in FIG. 5B that has the circuit of the semiconductor die 36. Here, after the other redistribution layer structure forming process, a second carrier wafer 82 different from the carrier wafer 80 is bonded to the other redistribution layer structure 72, and the carrier wafer 80 is peeled off, exposing a surface of the encapsulation layer 40 different from the surface on which the other redistribution layer structure 72 is formed. In other words, the stack can be inverted.

[0147] FIG. 5( c ) is a schematic cross-sectional view showing the state in which the first redistribution layer has been formed by the first redistribution layer formation step. By performing the first redistribution layer formation step on the surface of the sealing layer 40 of the laminate shown in FIG. 5( b ), a first redistribution layer having a first via structure can be formed. The first via structure can be formed, for example, so as to contact the conductive through via 37. Furthermore, a polishing step of polishing the surface of the first redistribution layer may be further included between the first redistribution layer formation step and the conductive portion formation step. In this way, by polishing the surface of the first redistribution layer before forming the conductive portion, it is possible to reduce the flatness value of the conductive portion. Furthermore, the flatness value of the conductive portion can also be adjusted by adjusting the composition, physical properties, etc. of the first insulating pattern-forming composition used as needed in the first redistribution layer formation step. For example, this may be adjusted by using a polyimide with a low molecular weight contained in the composition, using a polyimide with low shrinkage upon curing, or using a polymerizable compound or other component with excellent compatibility with resins.

[0148] 5(d) is a schematic cross-sectional view showing a state in which a resist pattern 84 has been formed on the first redistribution layer. Conductive portions can be formed by forming a resist pattern in this manner, forming a metal layer by plating or the like, and then peeling off the resist pattern 84. After the conductive portions are formed, the conductive portions can be insulated from each other by further applying a first pattern-forming composition (conductive portion forming step). Here, by applying a first insulating pattern-forming composition after the conductive portions are formed, insulation between the conductive portions and formation of an insulating pattern in the second redistribution layer may be simultaneously achieved.

[0149] The laminate shown in FIG. 6 can be formed by further forming another redistribution layer and conductive portion on the laminate shown in FIG. 5(d). The laminate shown in FIG. 6 can be formed by stacking, in this order, a second redistribution layer 46 including a second via structure 28, a second conductive portion-containing layer 50 including a second conductive portion 48, a third redistribution layer 54 including a third via structure 52, a third conductive portion-containing layer 58 including a third conductive portion 56, and another redistribution layer 62 including another conductive pattern 60. The stacking method can follow the above-mentioned second redistribution layer formation process, third redistribution layer formation process, other redistribution layer formation process, and other conductive portion formation process. Here, in the projection plane in the depth direction of the first via structure, the bottom surface of the second via structure 28 overlaps with the top surface of the first via structure 16. Furthermore, in the projection plane in the depth direction of the second via structure, it is preferable that the bottom surface of the third via structure 52 overlaps with the top surface of the second via structure 28. Furthermore, the flatness of the surface of the conductive portion on the side of the second via structure is 2 μm or less. The flatness of the surface of the second conductive portion on the side of the via structure is preferably 2 μm or less. The flatness of the surface of the third conductive portion on the side of the via structure is preferably 2 μm or less. Such flatness can be obtained by performing the polishing process described above on the core redistribution layer or by appropriately designing the composition for forming the insulating pattern as described above. Furthermore, a conductive connection 30 is formed on the surface of the other redistribution layer 62 by the conductive connection formation process.

[0150] Figure 7 is a schematic cross-sectional view showing a state in which another semiconductor die has been bonded to the stack shown in Figure 6. The stack shown in Figure 7 is obtained by adhering a third carrier wafer 86 to the rewiring stack structure of the stack shown in Figure 6, peeling off the second carrier wafer 82, forming connection portions 76 to other connection pads 74 connected to the other rewiring stack structure 72, and then bonding another semiconductor die 78 (another semiconductor die bonding step). The other connection pads 74 may be formed at this stage or may be formed in the other rewiring stack structure forming step described above.

[0151] The stack shown in FIG. 4 is obtained by peeling off the third carrier wafer 86 from the stack shown in FIG. 7, forming conductive connections on the connection pads 30, and bonding to a substrate.

[0152] The first insulating pattern-forming composition (composition) will be described in detail below.

[0153] The composition may be any known composition used in forming insulating patterns without any particular limitation, but preferably contains at least one resin selected from the group consisting of heterocycle-containing polymers and their precursors (hereinafter also referred to as "specific resin"), and more preferably contains at least one resin selected from the group consisting of polyimides and polyimide precursors. The imidization rate of the polyimide precursor is preferably less than 50%. The imidization rate of the polyimide is preferably 50% or more. Details of the imidization rate will be described later.

[0154] <Specific Resin> The heterocycle-containing polymer 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 heterocycle-containing polymers include polyimide, polybenzoxazole, and polyamideimide. A precursor of a heterocycle-containing polymer refers to a resin whose chemical structure changes upon external stimulation to become a heterocycle-containing polymer. A resin whose chemical structure changes upon heating to become a heterocycle-containing polymer is preferred, and a resin whose ring structure is formed by a ring-closing reaction upon heating to become a heterocycle-containing polymer is more preferred. Examples of precursors of heterocycle-containing polymers include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. That is, the 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 composition preferably contains, as the specific resin, polyimide or a polyimide precursor. Furthermore, the specific resin is preferably a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by formula (2) described below and a repeating unit represented by formula (4) described below. The specific resin preferably has a polymerizable group, more preferably a radically polymerizable group. When the specific resin has a radically polymerizable group, the composition preferably contains a radical polymerization initiator, more preferably a radical polymerization initiator and a radical crosslinking agent. Furthermore, if necessary, a sensitizer may be contained. From such a 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 composition preferably contains a photoacid generator. From such a 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 A ２ 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 ３are each independently a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and the four benzene rings described in formula (71) may each have a hydrogen atom substituted with a substituent. In this specification, a bond crossing a side of a ring structure means that one of the hydrogen atoms in the ring structure is substituted. In formula (72), * represents a bonding site with the nitrogen atom in formula (2).

[0165] In formula (71), A １ ~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 Preferably, it is -, -NHC(=O)-, or a group consisting of a combination of two or more thereof, more preferably 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, and even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-. In particular, A 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). １１１ is 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 in the three benzene rings described in formula (81), each hydrogen atom may be substituted with 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 １１２represents 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 the hydrogen atoms of each of the four benzene rings described in formula (7) may be substituted with a substituent. 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 (7-1). １ ~A ３ and the preferred embodiments of the substituents on the benzene ring are the same as those.

[0171] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５The 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 The preferred range of R in formula (2) is １１５ The same applies to the preferred range.

[0172] 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.

[0173] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0174] 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.

[0175] 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.

[0176]

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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).

[0185] 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).

[0186] - Cyclization rate (imidization rate) - From the viewpoint of the film strength, insulating properties, etc. of the resulting organic film, the cyclization rate (imidization rate) of the polyimide precursor is preferably less than 50%, more preferably 40% or less, even more preferably 30% or less, and even more preferably 20% or less. The lower limit of the cyclization rate is not particularly limited, and it is sufficient as long as it is 0%. The cyclization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide precursor is measured, and the absorption peak at 1377 cm due to the imide structure is detected. －１ Next, the polyimide precursor 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 1377 cm －１ The peak intensity P2 around the peak intensity P1 is measured. The cyclization rate of the polyimide precursor can be calculated using the obtained peak intensities P1 and P2 according to the following formula: Cyclization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[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 composition contains multiple polyimide precursors as the specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the 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 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 １３２or 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 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 １３１Examples 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 ２１In 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). ２１ The 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. １３１The 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, 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 １３１The 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). In formula (4-2), R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group 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. １３１ The 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 １３１is 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] Also, R １３１ is preferably a group containing a group represented by formula (2-1), and more preferably a group represented by formula (2-1). In formula (2-1), R １ and R ２ each independently represents a group having an ethylenically unsaturated bond, L represents a single bond or a divalent linking group not containing an imide bond, and * represents a bonding site to another structure.

[0207] In formula (2-1), R １ and R ２ are each preferably independently a group represented by the following formula (R1-1): In formula (R1-1), L Ｒ１ represents an (n+1)-valent linking group, R Ｒ１ R each independently represents an aromatic group directly bonded to a vinyl group, a maleimide group, a (meth)acryloxy group, or a (meth)acrylamide group, n represents an integer of 1 to 10, and * represents the bonding site with the oxygen atom in formula (2-1). Ｒ１are each independently preferably an aromatic group or a maleimide group directly bonded to a vinyl group, and more preferably a vinylphenyl group. Ｒ１ is a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, —S—, —S(═O) ２ - and -NR Ｎ - is preferably a group represented by a bond to at least one group selected from the group consisting of a hydrocarbon group, * １ -C(=O)-L Ｒ２ -* ２ Or, * １ -C(=O)NR Ｎ -L Ｒ２ -* ２ Preferably, the L is a group represented by the following formula: Ｒ１ The hydrocarbon group in the above L is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. Ｒ２ represents a hydrocarbon group, and is preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms. Ｎ The preferred embodiments of the above are as described above. １ has the same meaning as * in formula (R1-1), ２ is R in formula (R1-1) Ｒ１ represents the binding site with R Ｒ１ is a vinylphenyl group, L Ｒ１ is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group. Ｒ１ is a maleimide group, L Ｒ１ is an alkylene group having 1 to 4 carbon atoms or * １ -C(=O)-L Ｒ２ -* ２ It is preferable that R Ｒ１ is a (meth)acryloxy group or a (meth)acrylamide group, L Ｒ１ teeth* １ -C(=O)NR Ｎ -L Ｒ２ -* ２n is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0208] In formula (2-1), L is a single bond, —C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -S(=O) ２ - or a 9,9-fluorenediyl group is preferred. ３ ) ２ -, or -C(CF ３ ) ２ The embodiment in which - is also one of the preferred embodiments of the present invention.

[0209] 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.

[0210] R １３２ Examples of the tetracarboxylic acid residues include those remaining after removal of the anhydride groups from tetracarboxylic dianhydrides. １１５ From the viewpoint of the strength of the organic film, R １３２ is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0211] 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). １３２As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0212] 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.

[0213] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0214] In order to improve the storage stability of the 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.

[0215] -Imidization rate (ring closure rate)- The imidization rate of the polyimide (also referred to as "ring closure rate") is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less. The imidization rate is measured by the method described above.

[0216] Polyimide is a polymer in which all repeating units are R １３１ and R １３２The 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.

[0217] 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.

[0218] 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 composition contains multiple types of polyimides as the specific resin, 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 a single resin are each within the above ranges.

[0219] [Polybenzoxazole Precursor] Examples of the polybenzoxazole precursor include the compounds described in paragraphs 0073 to 0095 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0220] [Polybenzoxazole] Examples of polybenzoxazole include the compounds described in paragraphs 0101 to 0108 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0221] [Polyamideimide Precursor] Examples of the polyamideimide precursor include the compounds described in paragraphs 0104 to 0119 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0222] [Polyamideimide] Examples of polyamideimide include the compounds described in paragraphs 0125 to 0138 of WO 2022 / 145355, the disclosure of which is incorporated herein by reference.

[0223] [Method for Producing Polyimide Precursor, etc.] The polyimide precursor, etc., is produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022 / 145355. The above description is incorporated herein by reference.

[0224] [Content] The content of the specific resin in the composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the composition. Furthermore, the content of the resin in the composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the composition. The composition may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range.

[0225] It is also preferable that the composition contains at least two kinds of resins. Specifically, the composition 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 composition contains two or more kinds of specific resins. When the composition 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.

[0226] <Other Resins> The composition 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 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 polymerizable compound 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 composition, it is possible to improve the coatability of the composition and the solvent resistance of the pattern (cured product).

[0227] When the composition contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the composition. When the composition contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the composition. A preferred embodiment of the composition may have a low content of the other resin. 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 composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The composition 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.

[0228] <Polymerizable Compound> The composition preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0229] [Radical Crosslinking Agent] The composition preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the 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.

[0230] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably contains 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 composition contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0231] 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.

[0232] 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 polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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).

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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 of the *'s independently represents a hydrogen atom or a monovalent organic group, and each * 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. The inclusion of crosslinker U in a composition may improve chemical resistance, resolution, and the like. Crosslinker U may have only one urea bond or urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds. The total number of urea bonds and urethane bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinker U does not have a urethane bond, the number of urea bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinker U does not have a urea bond, the number of urethane bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0241] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (mass of the compound per mole of radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, still more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0242] The crosslinking agent U preferably has a structure represented by the following formula (U-1): In formula (U-1), R Ｕ１ represents a hydrogen atom or a monovalent organic group, and A represents —O— or —NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, and Z Ｕ２ is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0243] R Ｕ１ R is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Ｕ１ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ - is more preferred. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of these. R Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferred. Ｕ１Examples of the groups include those listed in 1. and preferred embodiments are also the same. X is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group, with a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group being preferred, and a (meth)acryloxy group being more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0244] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but an alcoholic hydroxy group is preferred. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, even more preferably an ethyleneoxy group or a propyleneoxy group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6. The amide group is represented by -C(=O)-NR Ｎ - refers to a bond represented by R Ｎ When the crosslinking agent U has an amide group, the crosslinking agent U may be, for example, R—C(═O)—NR Ｎ - a group represented by *, or *-C(=O)-NR ＮIt can be contained as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. Crosslinking agent U may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group is linked to at least one radically polymerizable group contained in crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when crosslinking agent U contains only one radically polymerizable group, it is preferred that the radically polymerizable group contained in crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred embodiments of the radical polymerizable group are the same as those of the radical polymerizable group in the crosslinking agent U.When crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred aspects of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. In the above aspect, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U have a hydroxy group.

[0245] From the viewpoint of compatibility with the heterocycle-containing polymer, etc., the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be condensed with other rings, for example, as in indole and benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in a linking group that links two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0246] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When crosslinking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond or urethane bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these objects via the shortest distance (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0247] [Axis of symmetry] It is also preferable that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry. The fact that the crosslinking agent U does not have an axis of symmetry means that the crosslinking agent U is a bilaterally asymmetric compound that does not have an axis that would produce a molecule identical to the original molecule by rotating the entire compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the fact that the crosslinking agent U does not have an axis of symmetry suppresses aggregation of the crosslinking agent U molecules in the composition film.

[0248] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0249] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0250] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0251] From the viewpoints of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl ... Examples of usable radical crosslinkers include 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 urethane bonds. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of approximately 200. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinker is preferably used as the radical crosslinker for the composition.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.

[0252] 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 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.

[0253] 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.

[0254] [Other Crosslinking Agents] The composition preferably contains another crosslinking agent different from the radical crosslinker described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinker described above. It is preferably a compound having multiple groups in its molecule that promote a reaction to form a covalent bond with other compounds in the composition or their reaction products upon exposure to light by the photoacid generator or photobase generator described above. It is also preferable for the compound to have multiple groups in its molecule that promote a reaction to form a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or 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.

[0255] [Polymerization initiator] The composition preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the composition contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, the composition may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0256] 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 －１ The 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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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).

[0261] 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).

[0262] 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.

[0263] 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.

[0264] 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.

[0265] 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 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.

[0266]

[0267] 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.

[0268] 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.

[0269] 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.

[0270] When the 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 solids content of the 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. Since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0271] [Sensitizer] The 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 benzophenones, Michler's ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethines, xanthenes, phthalocyanines, benzopyrans, and indigo 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.

[0272] When the 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 composition. The sensitizer may be used alone or in combination of two or more types.

[0273] [Chain Transfer Agent] The composition 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.

[0274] 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.

[0275] When the 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 composition. The chain transfer agent may be one type, or two or more types. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0276] In another preferred embodiment of the present invention, the composition contains two or more polymerization initiators. Specifically, the composition preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or the composition preferably contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0277] 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.

[0278] 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 %.

[0279] [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.

[0280] 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.

[0281] 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 composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. The 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.

[0282] <Base Generator> The composition 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 composition contains a heterocycle-containing polymer precursor, the composition preferably contains a base generator. By containing a thermal base generator in the composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good 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, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0283] Examples of the base generator include, but are not limited to, the following compounds:

[0284]

[0285] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0286] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0287] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0288] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0289] 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.

[0290] 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.

[0291] When the 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 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, still 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.

[0292] <Solvent> The composition 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.

[0293] 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.

[0294] 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.

[0295] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0296] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0297] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0298] 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.

[0299] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0300] 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.

[0301] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0302] In the present invention, the solvent is preferably 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, and more preferably contains at least one solvent selected from γ-butyrolactone, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. 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 solvents, is also a preferred embodiment of the present invention. In particular, from the viewpoint of storage stability of the 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 content may be determined in consideration of the solubility of components such as the heterocycle-containing polymer contained in the composition.Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

[0303] From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the composition of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 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.

[0304] <Metal Adhesion Improver> The composition preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used for 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.

[0305] [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.).

[0306]

[0307] 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.).

[0308] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0309] 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.

[0310] 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 heterocycle-containing polymer. 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.

[0311] <Migration Inhibitor> The composition preferably further contains a migration inhibitor. By including the migration inhibitor, for example, when the 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.

[0312] 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.

[0313] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0314] 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.

[0315] Specific examples of the migration inhibitor include the following compounds.

[0316]

[0317] When the composition 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 composition.

[0318] 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.

[0319] <Polymerization Inhibitor> The composition 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.

[0320] 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.

[0321] When the composition 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%, relative to the total solid content of the composition.

[0322] 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.

[0323] [Urea Compound, Carbodiimide Compound, Isourea Compound] From the viewpoint of elongation at break and adhesion to the metal or resin layer, the composition may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as "urea compound, etc."). Among these, it is preferable that the composition further contains a compound having a urea bond. The urea compound, etc. referred to here does not include the above-mentioned polymerizable compounds and compounds corresponding to silane coupling agents. Examples of urea compounds include the compounds described in paragraphs 0334 to 0339 of WO 2022 / 070730.

[0324] Specific examples of the urea compound include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0325] The total content of the urea compound and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the heterocycle-containing polymer. The urea compound and the like may be used alone or in combination of two or more types. When two or more types of bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof is within the above range.

[0326] <Transmittance Adjuster> The composition preferably contains a transmittance adjuster that adjusts the transmittance of exposure light. By including a transmittance adjuster, it becomes possible to favorably adjust the pattern shape of the resulting cured product. Examples of the transmittance adjuster include naphthoquinone diazide compounds, dyes whose absorbance changes upon exposure, photopolymerization initiators, photoacid generators, photobase generators, and sensitizers. Among these, the transmittance adjuster preferably contains at least one compound selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[0327] Examples of naphthoquinone diazide compounds 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.

[0328] The dye whose absorbance changes upon exposure is not particularly limited, and for example, known photochromic compounds can be used, including leuco dyes, diarylethene dyes, fulgides, spirooxazines, spiropyrans, azobenzene-based compounds, etc. Examples of leuco dyes include triarylmethane-based (e.g., triphenylmethane-based), spiropyran-based, fluoran-based, diphenylmethane-based, rhodamine lactam-based, indolylphthalide-based, and leucoauramine-based leuco dyes.

[0329] A photochromic compound is a compound whose absorption spectrum changes as a result of a change in the geometric structure of its molecule due to the absorption of light. Specific examples of spiropyran compounds, diarylethene compounds, and other photochromic compounds are shown below, but the present invention is not limited thereto.

[0330] Examples of the photobase generator include nifedipine compounds. As the nifedipine compound, a compound that generates a pyridine structure or a pyridinium salt structure by the action of light is preferred. Specific examples of nifedipine compounds are shown below, but the present invention is not limited thereto.

[0331] Examples of the sensitizer include coumarin compounds, etc. Specific examples of the coumarin compound include, but are not limited to, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin.

[0332] The content of the transmittance adjuster relative to the total solid content of the composition 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 %.

[0333] <Other Additives> The composition may contain various additives, as needed, within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.). By appropriately incorporating these components, it is possible to adjust properties such as film physical properties. 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 composition.

[0334] <Characteristics of the composition> The viscosity of the composition can be adjusted by the solid content concentration of the composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is less than 1 / s, a coating film with excellent surface condition can be obtained.

[0335] The Young's modulus of a coating film formed by applying the composition after heating at 230° C. for 2 hours is preferably 2.5 GPa or more. The Young's modulus is preferably 2.8 GPa or more, and more preferably 3.0 GPa or more. The upper limit of the Young's modulus is not particularly limited, but is preferably 10.0 GPa or less, for example.

[0336] Here, the coating method of the composition in measuring the Young's modulus is not particularly limited, and any method can be used as long as the distance from the substrate to the film surface (i.e., the coating film thickness) is, for example, 20 μm, and spin coating method can be used.In addition, if it is difficult to form a film with a distance of 20 μm by one spin coating method, spin coating method can be carried out multiple times.In addition, if it is still difficult to form a film with a distance of 20 μm by spin coating method, the coating method can be appropriately selected from known methods such as dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, slit coating method, inkjet method, etc.

[0337] If the composition contains a solvent, it is preferable to dry the composition after application. In this case, the distance from the substrate to the dried film surface is 20 μm. Drying is preferably performed until the amount of solvent in the film is 0.5% by mass or less. Drying conditions are not particularly limited, but drying by heating is possible. Furthermore, if sufficient drying is difficult to achieve by heating alone, further reduction in pressure may be performed. Drying can be performed in the atmosphere. However, if the composition contains components that are easily denatured by oxygen, drying can also be performed under inert gas such as nitrogen or under vacuum. Drying means are not particularly limited, but examples include a hot plate. However, if the above-mentioned reduction in pressure or inert gas replacement is required, an oven with a reduction in pressure function or an oven with a gas replacement function can also be used. When drying by heating, the heating temperature (drying temperature) can be, for example, 100°C. However, if drying at 100°C is difficult, the drying temperature may be appropriately changed between 70°C and 130°C, preferably between 90°C and 120°C, depending on the type of solvent contained in the composition. When drying by heating, the drying time (the time exposed to the above heating temperature) can be, for example, 5 minutes. However, if drying within 5 minutes is difficult, the drying time may be appropriately changed between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the composition, etc. When drying by heating, the temperature rise rate during heating is not particularly limited and can be, for example, 5°C / min. If drying at the above temperature rise rate is difficult, the temperature rise rate may be appropriately changed between 1 to 12°C / min or between 2 to 10°C / min, depending on the type of solvent contained in the composition, etc.

[0338] The coating film obtained by the above coating and optional drying is heated at 230°C for 2 hours to form a cured product. The composition film obtained by application is heated while avoiding exposure to light as much as possible. Contact with solvents such as developing solutions is also avoided as much as possible. The heating can be performed in an oven under a nitrogen atmosphere. The pressure during the heating is 1 atmosphere (101,325 Pa). The heating rate can be, for example, 10°C / min. If drying at the above heating rate is difficult, the heating rate may be appropriately changed between 1 and 12°C / min or between 2 and 10°C / min depending on the type of solvent contained in the composition. The heating time (time exposed to 230°C) during the heating is 2 hours. The Young's modulus of the cured product is measured after cooling the cured product to 25°C. The Young's modulus is measured by a tensile test. Specifically, the Young's modulus was measured in accordance with JIS-K7161-1 (2014) using a DMA850 (TA Instruments) at a crosshead speed of 5 mm / min under an environment of 25°C and 65% RH (relative humidity).

[0339] <Restrictions on substances contained in the composition> The water content of the composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the composition is improved. Furthermore, the lower limit of the water content of the resin composition is preferably 0.001% by mass or more, and can be 0.05% by mass or more, and can be 0.5% by mass or more, from the viewpoints of reducing the effort required for managing storage conditions, adhesion, developability, etc. Specific examples of the water content of the resin composition include 0.01% by mass, 0.4% by mass, and 1.8% by mass. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0340] From the viewpoints of insulation, reliability, etc., the metal content of the composition is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoints of reducing the effort required to reduce the metal content, mechanical properties, adhesion, etc., the lower limit of the metal content in the resin composition can be 0.001 ppm by mass or more, and can also be 0.01 ppm by mass or more. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, and tin, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total of these metals is within the above range. Specific examples of the metal content include 0.001 ppm by mass, 0.1 ppm by mass, and 0.7 ppm by mass.

[0341] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the composition include selecting raw materials with a low metal content as raw materials constituting the composition, filtering the raw materials constituting the composition, and lining the inside of an apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0342] Considering the use of the composition as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Among these, halogen atoms present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoint of reducing the effort required for reducing halogen ions, the lower limit of halogen ions in the resin composition can be 0.001 ppm by mass or more, and can also be 0.1 ppm by mass or more. Specific examples of the amount of halogen ions include 0.005 ppm by mass, 0.3 ppm by mass, and 1.6 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the halogen atom content include ion exchange treatment.

[0343] A conventionally known container can be used as the container for storing the composition. For the purpose of preventing impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0344] <Preparation of Composition> The composition can be prepared by mixing the above components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0345] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the composition. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtering and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the composition filled in a bottle may be placed under reduced pressure and subjected to a degassing process.

[0346] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0347] <Resin Synthesis> [Synthesis Example: Synthesis of Polymer 1] 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 70 g of N-methylpyrrolidone (NMP). Subsequently, 3.81 g (17.6 mmol) of 3,3'-dihydroxybenzidine and 3.74 g (17.6 mmol) of 2,2'-dimethylbenzidine were dissolved in 50 g of NMP and added dropwise over 1 hour at a temperature of 10°C to 25°C. After stirring at 25°C for 30 minutes, 10 g of toluene was added and the mixture was reacted at 200°C for 4 hours under a nitrogen flow and then cooled to 25°C. Subsequently, 15.3 g (50 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at 95°C for 15 hours, then cooled to 25°C and diluted with 120 g of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water and filtered, then reslurried again in 1 L of methanol and filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added thereto. The mixture was stirred for 4 hours, and the ion exchange resin was removed by filtration. After that, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried at 45°C under reduced pressure for 1 day to obtain Polymer 1. Polymer 1 is a resin having a repeating unit represented by the following formula. The subscripts in parentheses of the following repeating units represent the molar ratio of each repeating unit. The structure of the repeating unit is １ The weight average molecular weight of Polymer 1 was determined from the H-NMR spectrum. The weight average molecular weight was 25,000, the number average molecular weight was 10,500, and the imidization rate was 99% or more.

[0348] [Synthesis Example: Synthesis of Polymer 2] - Synthesis of Diamine 2a for Polymer 2 Synthesis - 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a flask. Under ice cooling, 98.21 g (450 mmol) of di-t-butyl dicarbonate was added dropwise. After the addition was completed, the mixture was stirred at 60°C for 5 hours. After the reaction was completed and the mixture was cooled to room temperature, 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 68.68 g (450 mmol) of p-chloromethylstyrene, 74.63 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added, and the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the mixture was filtered by suction filtration, and the filtrate was added dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was collected by suction filtration. The obtained white solid was purified by recrystallization using 1000 mL of acetone at 60°C. 125 g (yield 85.6%) of the following intermediate 2b was obtained. The structure of 2b is shown below. １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)8.04-7.94(s,2H), 7.75-7.64(d,2H), 7.56-7.42(m,8H), 7.27-7.20(d,2H), 7.19-7.12(d,2H), 6.79-6.64(2H), 5.89-5.77(2H), 5.30-5.15(6H), 1.49-1.43(s,18H)

[0349] 75.0 g (115.6 mmol) of 2b and 500 mL of methylene chloride were mixed in a 1 L flask. 131.8 g (1156 mmol) of trifluoroacetic acid was added at room temperature, and the mixture was stirred at 40°C for 5 hours. After the reaction was completed, 250 mL of methanol was added dropwise under ice cooling, followed by 117.0 g (1156 mmol) of triethylamine. Pale yellow crystals were precipitated, and the precipitated solid was collected by suction filtration. The mixture was suspended and washed in 750 mL of methanol, yielding 40.5 g (73% yield) of (2a). The structure of 2a is shown below. The following structure is １ This was confirmed by H-NMR spectrum.１ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)7.53-7.45(s,8H), 7.05-6.98(d,2H), 6.92-6.85(d,2H), 6.79-6.63(4H), 5.89-5.78(d,2H), 5.29-5.22(d,2H), 5.20-5.13(s,4H), 4.92-4.64(4H)

[0350] Synthesis of Polymer 2: 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 5.50 g (25.9 mmol) of 2,2'-dimethylbenzidine and 11.62 g (25.9 mmol) of 2a were dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at a temperature of 0 to 10°C. After stirring at 25°C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added and the mixture was reacted at 80°C for 4 hours. After completion of the reaction, the mixture was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, and after stirring for 15 minutes, the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40 ° C for 10 hours. Subsequently, the dried resin was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was obtained by filtration and dried under reduced pressure at 45 ° C for 1 day to obtain polymer 2. Polymer 2 is a resin having a repeating unit represented by the following formula. The subscripts in parentheses of the following repeating units represent the molar ratio of each repeating unit. The weight average molecular weight of polymer 2 was 25,000, the number average molecular weight was 12,500, and the imidization rate was 99% or more. １ Determined from H-NMR spectrum.

[0351] [Synthesis Example: Synthesis of Polymer 5 to Polymer 7] Polymer 5 to Polymer 7 were synthesized in the same manner as for Polymer 2, except that the raw materials used were changed appropriately. Polymer 5 to Polymer 7 are resins each having a repeating unit represented by the following formula. The structure of each repeating unit is: １ The molecular weights were determined from H-NMR spectra. In the structures below, the subscripts in parentheses indicate the molar ratios of each structure. The weight-average molecular weights, number-average molecular weights, and imidization ratios of these resins are shown in the tables below.

[0352]

[0353] Synthesis Example: Synthesis of Polymer 3 10.4 g (47.6 mmol) of pyromellitic anhydride, 10.6 g (20.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at a temperature of 60°C for 5 hours to produce a diester of pyromellitic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), and 2-hydroxyethyl methacrylate. The mixture was then cooled to -20°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 19.3 g (60.5 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. 10.0 g (217 mmol) of ethanol was then added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain a polyimide precursor (Polymer 3). The resulting polyimide precursor (polymer 3) had a weight-average molecular weight (Mw) of 25,000 and a number-average molecular weight (Mn) of 10,000. The polyimide precursor (polymer 3) is presumed to have a structure containing two repeating units represented by the following formula (polymer 3). The subscripts in parentheses of the following repeating units represent the molar ratio of each repeating unit. The weight-average molecular weight of polymer 3 was 25,000, the number-average molecular weight was 10,000, and the imidization rate was less than 5%.

[0354] Synthesis Example: Synthesis of Polymer 4 7.43 g (34.0 mmol) of pyromellitic anhydride, 17.7 g (34.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at a temperature of 60°C for 5 hours to produce a diester of pyromellitic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), and 2-hydroxyethyl methacrylate. The mixture was then cooled to -20°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 12.7 g (59.8 mmol) of 2,2'-dimethylbenzidine dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. 10.0 g (217 mmol) of ethanol was then added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain a polyimide precursor (Polymer 4). The resulting polyimide precursor (polymer 4) had a weight-average molecular weight (Mw) of 25,000 and a number-average molecular weight (Mn) of 9,950. The polyimide precursor (polymer 4) is presumed to have a structure containing two repeating units represented by the following formula (polymer 4): The subscripts in parentheses of the following repeating units indicate the molar ratio of each repeating unit. Polymer 4 had a weight-average molecular weight of 25,000, a number-average molecular weight of 9,950, and an imidization rate of less than 5%.

[0355] [Synthesis Example: Synthesis of Polymer 8] 23.5 g (75.7 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.3 g (75.7 mmol) of bisphthalic dianhydride (BPDA) were placed in a separable flask, and 39.7 g of 2-hydroxyethyl methacrylate (HEMA) and 136.8 g of tetrahydrofuran were added and stirred at room temperature (25°C). 24.7 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours. Next, under ice cooling, a solution of 62.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.6 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring, followed by 27.6 g (137.8 mmol) of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.7 g of tetrahydrofuran, which was then added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, followed by the addition of 136.8 g of tetrahydrofuran. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 716.2 g of ethanol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was filtered off and dissolved in 403.5 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 8470 g of water to precipitate the polymer, and the resulting precipitate was filtered off. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain a polyimide precursor (polymer 8). The resulting polyimide precursor (polymer 8) had a weight average molecular weight (Mw) of 25,300 and a number average molecular weight (Mn) of 10,150. The polyimide precursor (polymer 8) is presumed to have a structure containing two repeating units represented by the following formula (polymer 8). The subscripts in parentheses of the following repeating units represent the molar ratio of each repeating unit. The weight average molecular weight of polymer 8 was 25,000, the number average molecular weight was 10,150, and the imidization rate was 20%.

[0356] [Synthesis Example: Synthesis of Polymers 9 to 15] Polymers 9 to 15 were synthesized in the same manner as for Polymer 4, except that the raw materials used were changed appropriately. Polymers 9 to 15 are resins each having a repeating unit represented by the following formula. The structure of each repeating unit is: １ The molecular weights were determined from H-NMR spectra. In the structures below, the subscripts in parentheses indicate the molar ratios of each structure. The weight-average molecular weights, number-average molecular weights, and imidization ratios of these resins are shown in the tables below.

[0357]

[0358] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a first insulating pattern-forming composition. In each comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "parts by mass" column in each column of the table. The obtained first insulating pattern-forming composition and comparative composition were pressure-filtered using a polypropylene filter with a pore width of 0.45 μm. In the table, "-" indicates that the composition did not contain the corresponding component.

[0359]

[0360]

[0361] Details of each component listed in the table are as follows:

[0362] [Polymers (resins)] Polymers 1 to 15: Polymers 1 to 15 synthesized above

[0363] [Polymerizable Compounds] Polymerizable compound 1: Compound having the following structure Polymerizable compound 2: Compound having the following structure (in the following structures, the numbers represent the molar ratio of each structure contained.)

[0364] [Polymerization initiators] Polymerization initiators 1 to 4: compounds having the following structures

[0365] [Migration inhibitor] Migration inhibitor 1: Compound having the following structure

[0366] [Metal adhesion improver] Metal adhesion improver 1-2: Compounds having the following structure

[0367] [Light absorber] Light absorber 1: Compound having the following structure Light absorber 2: 1 to 2: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid (NQD (naphthoquinonediazide))

[0368] [Organotitanium Compounds] Organotitanium Compound 1: Compound having the following structure Organotitanium Compound 2: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0369] [Polymerization inhibitor] Polymerization inhibitors 1 and 2: compounds having the following structures

[0370] [Base Generator] Base Generator 1: Compound having the following structure

[0371] [Solvents] Solvent 1: GBL (γ-butyrolactone) Solvent 2: NMP (N-methyl-2-pyrrolidone) Solvent 3: DMSO (dimethyl sulfoxide) Solvent 4: EL (ethyl lactate)

[0372] <Evaluation> [Evaluation of Flatness] The composition prepared in each example was applied to a 300 mm silicon wafer, and then exposed to 300 mJ / cm 2 using a Canon exposure machine (FPA-5520iV LF). ２ After exposure to i-line light, the film was developed with cyclopentanone for 15 seconds and rinsed with PGMEA for 30 seconds to remove the unexposed areas. Exposure was performed through a photomask with circular unexposed areas of 9 μm in diameter. ２The curing treatment was carried out in an oven at 230°C for 3 hours, resulting in a pattern with a film thickness of 7 μm and a via bottom diameter of 9 μm. In Comparative Example 1, the same composition as in Example 12, Comparative Example 2, Example 13, and Comparative Example 3, Example 14, was used to obtain a pattern with a film thickness of 7 μm and a via bottom diameter of 9 μm, using the same method as above. After RIE plasma treatment using a wafer plasma cleaner (Samco PC-100), a 50 nm titanium layer and then a 200 nm copper layer were formed on the cured film using a batch sputtering system (ULVAC SV-200). A 7 μm thick coating was then formed using an i-line positive resist (Tokyo Ohka Kogyo Co., Ltd. ZR8800), which was then exposed using the stepper and developed for 70 seconds using a 2.38 wt% TMAH (tetraammonium hydroxide) aqueous solution, resulting in a 15 μm line spacing and 400 μm pitch pattern. Subsequently, copper plating was performed to form a 9 μm thick copper film using electrolytic copper plating. After stripping the positive resist, the copper sputtered layer (WLC-C2, manufactured by Mitsubishi Gas Chemical Co., Inc.) was etched, followed by etching of the titanium sputtered layer (MelStrip TI-3991, manufactured by Meltex) to plate 9 μm vias on the cured film. A first wiring layer (first rewiring layer and conductive portion) including an LS pattern with a thickness of 2 μm was formed on the vias and cured film. In examples marked "Yes" in the "CMP process" column of the table, the laminate surface was polished for 3 minutes at a pressure of 3 psi using a CMP (Chemical Mechanical Polishing) system manufactured by Fujikoshi Machinery Co., Ltd., with silica slurry (NP6220, manufactured by Nitta DuPont Co., Ltd.) to achieve a flat surface. To further form a second wiring layer, a RIE plasma treatment was performed using a wafer plasma cleaner (PC-100 manufactured by Samco), followed by a batch sputtering system (SV-200 manufactured by ULVAC, Inc.) to form a 50 nm titanium layer and then a 200 nm copper layer on the cured film. Thereafter, a 7 μm thick coating film was formed using an i-line positive resist (ZR8800 manufactured by Tokyo Ohka Kogyo Co., Ltd.), which was then exposed using the stepper and developed for 70 seconds using a 2.38 mass % TMAH aqueous solution to obtain an exposed pattern with an LS of 15 μm and a pitch of 400 μm. Subsequently, a 9 μm thick copper film was formed by electrolytic copper plating.After stripping the positive resist, the copper sputtered layer was etched (WLC-C2, manufactured by Mitsubishi Gas Chemical Co., Inc.), followed by etching the titanium sputtered layer (MelStrip TI-3991, manufactured by Meltex) to plate 9 μm vias in the cured film. A second wiring layer (first rewiring layer and conductive portion) including an LS pattern was formed with a thickness of 2 μm on the vias and the cured film. Figure 8 is a schematic cross-sectional view of the laminate formed in this example. In Figure 8, a first rewiring layer including a first via structure 202 and a first insulating pattern (cured product) 204 is formed on a silicon wafer 200. A conductive portion 206 is formed on the first rewiring layer, and a second via structure 208 is formed thereon. The conductive portion 206 and the second via structure 208 are arranged between the patterns of a second insulating pattern 210. A second conductive portion 212 is formed on the second via structure 208. Here, in a projection plane in the depth direction of the first via structure 202, the top surface of the first via structure 202 and at least a portion of the bottom surface of the second via structure 208 overlap, and the top surface of the first via structure 202 and the bottom surface of the second via structure 208 in the overlapping region are connected by a conductive portion 206. The flatness of the surface of the LS pattern of the formed second wiring layer was confirmed using an SEM to evaluate the flatness. Here, flatness is defined as the difference between the maximum and minimum distances from the wafer surface to the surface of the conductive portion of the LS pattern. The evaluation criteria were: flatness of 1.0 μm or less was rated 3, flatness of 2.0 μm or less was rated 2, and flatness of more than 2.0 μm was rated 1.

[0373] [Evaluation of Reliability] In each example or comparative example, a laminate was produced by the same method as that described in the "Evaluation of Flatness" above. The resulting laminate was subjected to a TCT test (ES-57L manufactured by Hitachi Global Life Solutions, Inc., 1000 cycles of temperatures between -55°C and 150°C). The presence or absence of cracks at the interface between the Cu wiring and the cured product in the VIA pattern portion of the first wiring portion was observed using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation). Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "TCT" column in the table. (Evaluation criteria) 3: 0 cracks were observed out of 10 observed locations. 2: 1 to 3 cracks were observed out of 10 observed locations. 1: Cracks were observed in all 10 observed locations.

[0374]

[0375] From the above results, it can be seen that the laminate of the present invention is excellent in reliability. The inventions according to Comparative Examples 1 to 3 have low flatness. It can be seen that such embodiments have poor reliability.

[0376] [Evaluation of Taper Angle] Each of the resin compositions and comparative compositions prepared in each Example and Comparative Example was applied in the form of a layer by spin coating to the surface of a thin copper layer of a resin substrate having a thin copper layer formed on the surface thereof, and dried on a hot plate at 110°C for 3 minutes to form a resin composition layer having a thickness of 5 μm after film formation. The resin composition layer was then exposed using a stepper (FPA-3000 i5 (manufactured by Canon Corporation)). The exposure was performed using a mask having a hole pattern of 5 μm diameter formed at 1 μm intervals, with a wavelength of 365 nm and a density of 400 mJ / cm. ２ The resist was then developed with cyclopentanone for 15 seconds, rinsed with PGMEA for 30 seconds, and heated at 230°C for 1 hour at a heating rate of 10°C / min in a nitrogen atmosphere to obtain a 5 μm hole pattern. The taper angle of the cross-sectional shape of the hole pattern was measured using a scanning electron microscope (SEM), and the taper angle was found to be within the range of 80 to 85° in all examples.

[0377] [Measurement of elongation (elongation at break)] In each example and comparative example, a resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer having a uniform thickness of about 15 µm after film formation on the silicon wafer. The obtained resin composition layer was exposed to a Ushio exposure machine (light source: 500 W / m ２ Ultra-high pressure mercury lamp) at 400 mJ / cm ２ The resin composition layer was exposed to light using a dumbbell-shaped mask at an exposure energy of 100 keV. The dumbbell shape was a dumbbell No. 7 shape as described in JIS K 6251:2017. The exposed resin composition layer (resin layer) was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to remove unexposed areas. The temperature was then increased at a rate of 10°C / min under a nitrogen atmosphere, and the layer was heated to 230°C for 3 hours. The cured resin layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and a dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width: 2 mm, sample length: 35 mm). The obtained test specimens were subjected to longitudinal elongation measurement in accordance with JIS-K7161-1 (2014) using a tensile tester (Instron Model 5965) at a crosshead speed of 5 mm / min under an environment of 25°C and 65% RH (relative humidity). Each evaluation was performed six times, and the arithmetic mean value of the elongation at break was used as the value of the breaking elongation. In all examples, the breakage progression rate was within the range of 50% or more.

[0378] [Measurement of Young's Modulus] The Young's modulus of the test pieces prepared in the above elongation measurement was measured in accordance with JIS-K7161-1 (2014) using a DMA850 (TA Instruments) at a crosshead speed of 5 mm / min, 25 ° C., and 65% RH (relative humidity). In all examples, the Young's modulus was 2.7 GPa or more.

[0379] [Measurement of Glass Transition Temperature] The Tg of the test pieces prepared in the above elongation measurement was measured using a DMA850 (TA Instruments). Specifically, the temperature conditions of the cured product were changed in the following order (1) to (2), and the glass transition temperature was measured. (1) The temperature was increased from 25°C to 350°C at a rate of 5°C / min. (2) The temperature was cooled from 350°C to 25°C. In all examples, the Tg was 230°C or higher.

[0380] 10 Laminate 12 First insulating pattern 12 14 First conductive pattern 16 First via structure 18 Insulating pattern 20 Conductive pattern 22 Conductive portion 24 Second insulating pattern 26 Second conductive pattern 28 Second via structure 30 Connection pad 32 Top surface of first via structure 34 Bottom surface of second via structure 36 Semiconductor die 37 Conductive through via 38 Encapsulating material 40 Encapsulating layer 42 First redistribution layer 44 Conductive portion-containing layer 46 Second redistribution layer 48 Second conductive portion 50 Second conductive portion-containing layer 52 Third via structure 54 Third redistribution layer 56 Third conductive portion 58 Third conductive portion-containing layer 60 Other conductive pattern 62 Other redistribution layer 62 64 Conductive connection portion 66 Substrate 68 Electrode 70 Other connection portion 72 Another redistribution stack structure 74 Another connection pad 76 Connection portion 78 Another semiconductor die 80 Carrier wafer 82 Second carrier wafer 84 Resist layer 86 Third carrier wafer 102 Conductive connection portion 104 Conductive pad 106 Insulation pattern in outermost layer of redistribution stack structure 108 Conductive pattern in outermost layer of redistribution stack structure 110 Solder member 112 Pillar 200 Silicon wafer 202 First via structure 204 First insulating pattern 206 Conductive portion 208 Second via structure 210 Second insulating pattern 212 Second conductive portion

Claims

1. A laminate comprising: a first redistribution layer having a first insulating pattern and a first conductive pattern present between the first insulating patterns, the first redistribution layer including a first via structure as the first conductive pattern; and a second redistribution layer having a second insulating pattern and a second conductive pattern present between the second insulating patterns, the second redistribution layer including a second via structure as the second conductive pattern, wherein in a projection plane in a depth direction of the first via structure, an upper surface of the first via structure overlaps with at least a part of a bottom surface of the second via structure, the upper surface of the first via structure and the bottom surface of the second via structure in the overlapping region are connected by a conductive portion, and the flatness of the surface of the conductive portion facing the second via structure is 2 μm or less.

2. The stack of claim 1, further comprising an encapsulation layer including at least one semiconductor die and an encapsulant, the first redistribution layer being formed on the semiconductor die, and the first conductive pattern being electrically connected to the semiconductor die.

3. The laminate according to claim 1 or 2, further comprising a third redistribution layer having a third insulating pattern and a third conductive pattern present between the third insulating patterns, and including a third via structure as the third conductive pattern, wherein in a projection plane in the via depth direction, an upper surface of the second via structure overlaps with at least a portion of a bottom surface of the third via structure, the upper surface of the second via structure and the bottom surface of the third via structure in the overlapping region are connected by a second conductive portion, and the flatness of the surface of the second conductive portion facing the third via structure is 2 μm or less.

4. A laminate as described in claim 1 or 2, wherein the angle between the bottom surface of the first insulating pattern and the side surface of the first insulating pattern in the first via structure is greater than or equal to 80° and less than 90°.

5. The laminate according to claim 1 or 2, wherein the conductive portion includes a line and space pattern, and the minimum width of the conductive portion in the line and space pattern is 0.1 to 20 μm.

6. The laminate according to claim 1 or 2, wherein the first rewiring layer has a thickness of 0.1 to 20 μm.

7. The laminate according to claim 1 or 2, wherein the first conductive pattern has a barrier layer.

8. The laminate according to claim 1 or 2, wherein the first insulating pattern has a breaking elongation of 40% or more.

9. The laminate according to claim 1 or 2, wherein the glass transition temperature of the first insulating pattern is 230° C. or higher.

10. The laminate according to claim 1 or 2, wherein the Young's modulus of the first insulating pattern is 2.5 GPa or more.

11. A method for manufacturing a laminate, comprising: a first redistribution layer forming step of forming a first redistribution layer having a first insulating pattern and a first conductive pattern existing between the first insulating patterns, the first redistribution layer including a first via structure as the first conductive pattern; a conductive portion forming step of forming a conductive portion in contact with the first via structure; and a second redistribution layer forming step of forming a second redistribution layer having a second insulating pattern and a second conductive pattern existing between the second insulating pattern, the second redistribution layer including a second via structure in contact with the conductive portion as the second conductive pattern, wherein an upper surface of the first via structure and at least a part of a bottom surface of the second via structure overlap in a projection plane in a via depth direction, and the flatness of the surface of the conductive portion facing the second via structure is 2 μm or less.

12. The method for producing a laminate according to claim 11, further comprising a polishing step of polishing the surface of the first rewiring layer between the first rewiring layer forming step and the conductive portion forming step.

13. The method for producing a laminate according to claim 11 or 12, wherein the first redistribution layer forming step includes a film forming step of applying a first insulating pattern forming composition onto a substrate to form a film.

14. The method for producing a laminate according to claim 13, wherein the substrate comprises an encapsulation layer including at least one semiconductor die and an encapsulant, and in the film formation step, a first insulating pattern forming composition is applied onto the semiconductor die, and the first conductive pattern and the semiconductor die are formed so as to be electrically connected to each other.

15. The method for producing a laminate according to claim 13, wherein the first insulating pattern forming composition contains at least one resin selected from the group consisting of polyimide and polyimide precursors.

16. A method for producing a laminate as described in claim 13, comprising the steps of applying the composition for forming a first insulating pattern to a substrate to form a coating film, drying, exposing and developing the coating film to form a precursor pattern, and heating the precursor pattern to obtain a first insulating pattern, wherein the rate of change in film thickness of the first insulating pattern relative to the precursor pattern is less than 10%.

17. The method for producing a laminate according to claim 13, wherein the resin contains a polyimide having an imidization rate of 50% or more.

18. The method for producing a laminate according to claim 13, wherein a coating film formed by applying the composition has a Young's modulus of 2.5 GPa or more after heating at 230° C. for 3 hours.

19. The method for producing a laminate according to claim 13, wherein the resin contains a polyimide precursor having an imidization rate of less than 50%.

20. The method for producing a laminate according to claim 13, wherein the composition includes a transmittance control agent.

21. The method for producing a laminate described in claim 20, wherein the transmittance adjuster contains at least one compound selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

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