Method for manufacturing cured products, method for manufacturing laminates, method for manufacturing semiconductor devices, resin composition, cured product, laminate, and semiconductor device

Abstract

Provided are: a cured product manufacturing method whereby a cured product having excellent adhesion with metal can be obtained; a laminate manufacturing method that uses the cured product manufacturing method; and a semiconductor device manufacturing method. Provided are: a resin composition whereby a cured product having excellent adhesion with metal can be obtained; a cured product obtained by curing the resin composition; a laminate that includes the cured project; and a semiconductor device. This cured product manufacturing method includes a film forming step and a heating step for heating the film at a heating temperature of 180°C or lower. The film after the heating step is raised in temperature from 25°C to 260°C at a speed of 10°C / minute, is maintained at 260°C for 15 minutes, and the mass loss ratio when the temperature is raised from 260°C to 300°C at a speed of 10°C / minute is 15% or lower. The cyclization rate of a cyclized resin obtained from a precursor of the cyclized resin in the obtained cured product is 95% or higher.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a cured product, a method for manufacturing a laminate, a method for manufacturing a semiconductor device, a resin composition, a cured product, a laminate, and a semiconductor device. [Background technology]

[0002] Cyclic resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples in semiconductor devices for packaging include their use as insulating films, encapsulants, or protective films. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the applications described above, cyclized resins such as polyimide are used in the form of a resin composition containing at least one of the cyclized resin such as polyimide and a precursor of the cyclized resin. Such a resin composition can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. The precursors of the cyclized resin, such as polyimide precursors, are cyclized, for example, by heating, and become cyclized resins such as polyimide in the cured product. Since the resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, the industrial application development of the above-mentioned resin composition is increasingly expected from the standpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a semiconductor device comprising a semiconductor chip, a sealing material covering the semiconductor chip, and a redistribution layer having a larger area than the semiconductor chip in a plan view, characterized in that the weight loss rate of the interlayer insulating film of the redistribution layer after being heated to 700°C at a rate of 10°C / min in an air atmosphere is 5 to 95% by weight. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-113748 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In a method for obtaining a cured product by curing a resin composition containing a precursor of a cyclized resin, it is sometimes required that the resulting cured product exhibits excellent adhesion to metal. The present invention aims to provide a method for producing a cured product that exhibits excellent adhesion to metals, and a method for producing a laminate and a method for producing a semiconductor device using the above method for producing a cured product. Furthermore, the present invention aims to provide a resin composition that yields a cured product with excellent adhesion to metals, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, and a semiconductor device. [Means for solving the problem]

[0007] Examples of typical embodiments of the present invention are shown below. <1> A film-forming step involves applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and A method for producing a cured product, comprising a heating step of heating the above film at a heating temperature of 180°C or lower, The mass loss rate expressed by the following formula A when the film after the above heating process is heated from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then heated from 260°C to 300°C at a rate of 10°C / min is 15% or less. The cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the resulting cured product is 95% or higher. A method for manufacturing a cured product. Formula A: Mass loss rate (%) = {1 - (mass of the film after heating at 300°C) / (mass of the film at 25°C)} × 100 <2> If the heating temperature in the above heating process exceeds 150°C, <1> A method for producing the cured product described above. <3> The above mass reduction rate is 10% or less. <1> or <2> A method for producing the cured product described above. <4> The above mass reduction rate is 5% or less. <1> ~ <3> A method for producing a cured product as described in any one of the following. <5> The above cyclization rate is 98% or higher. <1> ~ <4> A method for producing a cured product as described in any one of the following. <6> The film after the above heating step is a polyimide film. <1> ~ <5> A method for producing a cured product as described in any one of the following. <7> The process further includes an exposure step for selectively exposing the film between the above film formation step and the above heating step. <1> ~ <6> A method for producing a cured product as described in any one of the following. <8> Between the exposure step and the heating step, the process further includes a developing step in which the exposed film is developed with a developing solution to form a pattern. <7> A method for producing the cured product described above. <9> The above developing solution contains an organic solvent. <8> A method for producing the cured product described above. <10> The above development process is the process of forming a negative-type pattern. <8> or <9> A method for producing the cured product described above. <11> The above developing solution contains a base. <8> ~ <10> A method for producing a cured product as described in any one of the following. <12> Between the above developing step and the above heating step, a processing step is included in which a processing solution containing a base is brought into contact with the above pattern. <8> ~ <11> A method for producing a cured product as described in any one of the following. <13> The above resin composition contains a photosensitive agent. <1> ~ <12> A method for producing a cured product as described in any one of the following. <14> The above resin composition contains a solvent, and the content of the cyclized resin precursor is 70% by mass or more relative to the total solid content of the resin composition. <1> ~ <13> A method for producing a cured product as described in any one of the following. <15> The above resin composition contains a polymerizable compound having a boiling point of 270°C or higher at 1 atmosphere. <1> ~ <14> A method for producing a cured product as described in any one of the following. <16> The method for producing a cured product according to <15>, wherein the polymerizable compound having a boiling point of 270 °C or higher at 1 atm is a compound having three or more (meth) acrylate groups. <17> The method for producing a cured product according to any one of <1> to <16>, wherein the content of the component having a molecular weight of 1000 or less and different from the solvent is 30% by mass or less based on the total solid content of the resin composition. <18> The precursor of the above-mentioned cyclized resin includes a resin having at least one of the repeating units represented by the following formula (1-1) and the repeating units represented by the following formula (1-2), <1> to <17> The method for producing a cured product according to any one of <1> to <17>.

Chemical formula

Chemical formula

[0008] The present invention provides a method for manufacturing a cured product that exhibits excellent adhesion to metals, and a method for manufacturing a laminate and a semiconductor device using the above method for manufacturing a cured product. Furthermore, the present invention provides a resin composition that yields a cured product with excellent adhesion to metals, a cured product obtained by curing the resin composition, a laminate containing the cured product, and a semiconductor device. [Modes for carrying out the invention]

[0009] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, a numerical range represented by the symbol "~" means a range that includes the numbers written before and after "~" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes insofar as they achieve their intended function. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids refers to the total mass of all components of the composition excluding the solvent. In this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values, unless otherwise specified, and are measured using gel permeation chromatography (GPC). In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, if THF is unsuitable as an eluent, such as in cases of low solubility, NMP (N-methyl-2-pyrrolidone) may be used. Furthermore, unless otherwise specified, detection in GPC measurements will be performed using a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that the other layer is above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component. Furthermore, unless otherwise specified, the content of each component in a composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a preferred combination of embodiments is a more preferred embodiment.

[0010] (Method of manufacturing a cured product) The present invention provides a method for producing a cured product, comprising a film-forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and a heating step of heating the film at a heating temperature of 180°C or lower, wherein the film after the heating step is heated from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then heated from 260°C to 300°C at a rate of 10°C / min, the mass loss rate represented by the following formula A is 15% or less, and the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the resulting cured product is 95% or more. Formula A: Mass loss rate (%) = {1 - (mass of the film after heating at 300°C) / (mass of the film at 25°C)} × 100

[0011] According to the method for producing a cured product of the present invention, a cured product with excellent adhesion to metal can be obtained. The mechanism by which the above effects are achieved is unknown, but it is speculated to be as follows. In the method for producing a cured product of the present invention, the heating temperature in the heating step is 180°C or lower, the film after the heating step is heated from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, heated from 260°C to 300°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and the mass loss rate when heated from 260°C to 300°C at a rate of 10°C / min is 15% or lower, and the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the resulting cured product is 95% or higher. Here, if the mass reduction rate is 15% or less, it is presumed that outgassing is suppressed, and therefore excellent adhesion between the cured material and the metal is considered to be achieved. Furthermore, if the cyclization rate is 95% or higher, it is thought that the migration of metal ions from the metal layer to the hardened product, using the uncyclized portion as a penetration path, is also suppressed. Due to these effects, it is believed that, according to the method for producing cured products of the present invention, even cured products obtained by heating at a low temperature of 180°C or below can be obtained with excellent adhesion to metal. Furthermore, the cured product obtained by the manufacturing method of the present invention is expected to have excellent moisture resistance because it has a high cyclization rate. The following describes in detail each step included in the method for producing the cured product of the present invention, as well as the physical properties of the cured product.

[0012] <Film formation process> The present invention's method for producing a cured product includes a film-forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film. Details of the above resin composition will be described later.

[0013] [Base material] The type of substrate can be appropriately determined depending on the application, but examples include semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin-film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs), and are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. Furthermore, these substrates may have layers on their surface, such as an adhesion layer or an oxidation layer, provided with hexamethyldisilazane (HMDS) or the like. Furthermore, the shape of the base material is not particularly limited and may be circular or rectangular. For the base material, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the shorter side is 100 to 1000 mm, preferably 200 to 700 mm. Furthermore, as the base material, for example, a plate-shaped, preferably panel-shaped, base material (substrate) is used.

[0014] Furthermore, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0015] As a means of applying the resin composition onto the substrate, coating is preferred.

[0016] Examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm. Alternatively, a method can be applied in which a coating film, which has been formed in advance on a temporary support using the above application method, is transferred onto a substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Publication No. 2006-047592 can be suitably used in the present invention as well. Furthermore, a process to remove excess film from the edges of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing. Alternatively, a pre-wetting process may be employed in which the substrate is coated with various solvents to improve its wettability before applying the resin composition to the substrate.

[0017] <Drying process> The above film may be subjected to a drying step (a process in which the formed film (layer) is dried in order to remove the solvent after the film formation step (layer formation step). In other words, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step. Furthermore, it is preferable that the above drying step be performed after the film formation step and before the exposure step. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0018] <Heating process> The method for producing the cured product of the present invention includes a heating step of heating the above film at a heating temperature of 180°C or lower. Here, the film in the heating step may be a developed film (pattern) that has gone through the exposure step and development step described later, or a film that has gone through the exposure step described later but has not gone through the development step, or a film that has been formed by the above-mentioned film formation step (and, if necessary, the above-mentioned drying step) and has not gone through any other steps. Furthermore, in the method for producing the cured product of the present invention, it is preferable that the temperature of the film is 180°C or lower throughout all steps, including the heating step. According to the above embodiment, it is possible to suppress thermal damage to materials such as the substrate. During the heating process, resins such as polyimide precursors undergo cyclization to become resins such as polyimide. Furthermore, during the heating process, crosslinking of unreacted crosslinkable groups in the specific resin or other crosslinking agents (described later) also proceeds. The heating temperature (maximum heating temperature) in the heating process is preferably 20°C to 180°C, more preferably 150°C to 180°C, and even more preferably 160°C to 180°C. In this process, the film after the heating step is preferably a polyimide film. Specifically, the resin contained in the film after the heating step is preferably a resin having an imide ring structure in its repeating units.

[0019] The heating step is preferably a step in which heating promotes the cyclization reaction of the precursor of the cyclizing resin within the film, and more preferably a step in which the cyclization reaction of the precursor of the cyclizing resin within the film is promoted by the action of a specific resin described later, or a base generated from a base generating agent, a base that has permeated from the developing solution, a base that has permeated from the rinsing solution, etc. In other words, it is preferable that the cyclization rate of the film after the heating process (i.e., the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin) increases before and after the heating process. Specifically, when the cyclization rate (%) of the film before the heating process is denoted as cyclization rate A, and the cyclization rate (%) of the film after the heating process is denoted as cyclization rate B, it is preferable that the difference in cyclization rates expressed by the following formula is 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above cyclization rate is not particularly limited and may be 100%. Difference in cyclization rate = Cyclization rate B - Cyclization rate A The method for measuring the cyclization rate of the film will be described later.

[0020] In the heating process, heating is preferably carried out at a heating rate of 0.1 to 30°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 0.5 to 20°C / minute, and even more preferably 2 to 10°C / minute. By setting the heating rate to 0.1°C / minute or higher, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or lower, residual stress in the cured product can be relieved. In addition, in the case of a rapid heating oven, it is preferable to raise the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 30°C / second, more preferably 2 to 20°C / second, and even more preferably 3 to 10°C / second.

[0021] The starting temperature for heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when a resin composition is applied to a substrate and then dried, this is the temperature of the film (layer) after drying. It is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0022] The heating time (heating time at the maximum heating temperature) is preferably 30 minutes to 5 hours, and more preferably 1 hour to 3 hours. Furthermore, the temperature fluctuation range when maintaining the maximum heating temperature (the difference between the maximum and minimum temperature during the heating time at the maximum temperature) is preferably 0.1°C to 20°C, more preferably 0.1 to 10°C, and even more preferably 0.1°C to 3°C.

[0023] 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, particularly preferably 120°C or higher, and most preferably exceeding 150°C. The upper limit of the above heating temperature is 180°C or lower.

[0024] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is best carried out for a short time, from about 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferable. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be performed in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 180°C. Furthermore, the mixture may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / minute.

[0025] The heating process is preferably carried out in a low-oxygen atmosphere by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating process may be carried out under atmospheric pressure or under reduced pressure. When heating is carried out under reduced pressure, the reduction may be completed before the start of heating, during the temperature rise from the start of heating, or after the maximum heating temperature is reached; the timing of the completion of the reduction is not particularly limited. Completion of the reduction means that the pressure becomes 20 mmHg (by volume) or less. The above pressure can be measured by a differential pressure gauge. It is also preferable that the film is under reduced pressure for the entire time that the maximum heating temperature is maintained. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0026] <Exposure process> After the film formation step and before the heating step, the film may be subjected to an exposure step in which the film is selectively exposed. In other words, the method for producing a cured product of the present invention may include an exposure step between the above-mentioned film formation step and the above-mentioned heating step, in which the film formed by the film formation step is selectively exposed to light. Selective exposure means exposing only a portion of a film. Selective exposure creates areas on the film that are exposed (exposed regions) and areas that are not exposed (unexposed regions). The exposure dose is not specifically defined as long as it can cure the resin composition, but for example, it can be 50 to 10,000 mJ / cm² in terms of exposure energy at a wavelength of 365 nm. 2 Preferably, 200-8,000 mJ / cm² 2 This is preferable.

[0027] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0028] In relation to the light source, the exposure wavelengths include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (g, h, i-line wavelengths), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic 532nm and third harmonic 355nm of YAG lasers. For resin compositions, exposure with a high-pressure mercury lamp is particularly preferred, and among these, exposure with the i-line is preferred. This can result in particularly high exposure sensitivity. Furthermore, the exposure method is not particularly limited; any method that exposes at least a portion of the film made of the resin composition is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0029] <Post-exposure heating process> The above film may be subjected to a heating step after exposure (post-exposure heating step). In other words, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed by the exposure step is heated. It is also preferable that the cyclization rate of the film after the heating process (i.e., the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin) does not substantially increase before and after the post-exposure heating process. Specifically, the difference in cyclization rates mentioned above is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The upper limit of the cyclization rate is not particularly limited and may be 0%. In particular, if the above film does not contain the photobase generator described later, the difference in cyclization rates described above is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The upper limit of the above cyclization rate is not particularly limited and may be 0%. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating process is preferably 1 to 12°C / min from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. Furthermore, the heating rate may be changed as needed during the heating process. The heating means in the post-exposure heating process is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0030] <Developing process> The film after exposure may be subjected to a developing process in which it is developed using a developing solution to form a pattern. In other words, the method for producing a cured product of the present invention may include a developing step in which the film exposed in the exposure step is developed using a developer to form a pattern. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed areas of the film are removed by the development process is called negative development, and the resulting pattern is called a negative pattern. Also, development in which the exposed areas of the film are removed by the development process is called positive development, and the resulting pattern is called a positive pattern. In the present invention, the developing step is preferably a step in which a negative-type pattern is formed.

[0031] [Developer] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents, with a developing solution containing an organic solvent being preferable.

[0032] When the developing solution is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, 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 are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, when using TMAH, for example.

[0033] If the developer contains an organic solvent, the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, alkyloxyacetate, alkyloxyacetate, alkyloxybutyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate) 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate) , ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and A Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as toluene, xylene, anisole, and other aromatic hydrocarbons, cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0034] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. 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 most preferred.

[0035] 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 above content may be 100% by mass. Furthermore, if the developer contains an organic solvent, the water content relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The above water content is not particularly limited and may be 0% by mass.

[0036] A preferred embodiment is one in which the developing solution contains at least one compound selected from the group consisting of bases and base generators. According to the above embodiment, it is believed that in the developing step, a base or base generator in the developing solution penetrates into the film, and in the subsequent heating step, the cyclization of the precursor of the cyclized resin is promoted by the action of the base generated from the base or base generator. As a result, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin after the heating process is increased, and it is believed that the adhesion between the metal and the cured product is improved even when heated at a low temperature of 180°C or below. In the above embodiment, from the viewpoint of long-term adhesion between the metal and the cured product, it is preferable that the developing solution contains a base. Furthermore, in the above embodiment, the developer is preferably a developer containing an organic solvent.

[0037] -base- As for preferred bases, organic bases are preferred from the viewpoint of reliability when they remain in the cured product (adhesion to the substrate when the cured product is further heated). Furthermore, as the base, a base having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, but in order to promote the imidation reaction, primary amines, secondary amines, and tertiary amines are preferred, secondary amines or tertiary amines are more preferred, and tertiary amines are most preferred. From the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferable that the base does not remain in the resulting cured product, and from the viewpoint of promoting cyclization (imidization), it is preferable that the amount remaining before heating does not decrease easily due to volatilization, vaporization, etc. Therefore, the boiling point of the base 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. Furthermore, the boiling point of the base is preferably higher than the boiling point of the organic solvent contained in the developer solution minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the developer solution. For example, if the boiling point of the organic solvent is 100°C, the base used is preferably one with a boiling point of 80°C or higher, and more preferably one with a boiling point of 100°C or higher.

[0038] The pKa of the conjugate acid of the above base in DMSO (dimethyl sulfoxide) is preferably 1 or higher, and more preferably 3 or higher. The upper limit of the above pKa is not particularly limited, but it is preferably 20 or lower. If the conjugate acid of the above base has multiple pKa values ​​in DMSO, it is preferable that at least one of them is within the above range. Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, and values ​​can be referenced from *Determination of Organic Structures by Physical Methods* (Authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and *Data for Biochemical Research* (Authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not listed in these publications, the value calculated from the structural formula using ACD / pKa (ACD / Labs) software will be used as the pKa.

[0039] Specific examples of bases contained in developing solutions include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, dimethylcyclohexylamine, 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, 1,5- Examples include diaminopentane, 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, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, etc.

[0040] If a base is present, the base content relative to the total mass of the developer is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. Furthermore, if the base is not a liquid at 10 to 30°C, the base content is preferably 0.3 to 30% by mass, and more preferably 0.5 to 20% by mass. A single base may be used, or two or more bases may be used in combination. When two or more bases are used in combination in the developing solution, it is preferable that their total content be within the range described above.

[0041] -Base Generator- The developing solution may contain a base-generating agent. Examples of base generators include photobase generators and thermal base generators, with thermal base generators being preferred. As the above-mentioned photobase generator or thermobase generator, for example, the base generator described later as a component included in the resin composition can be used without particular limitation.

[0042] If the developer contains a base generating agent, the amount of base generating agent relative to the total mass of the developer is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass, and even more preferably 0.08 to 5% by mass. The base generating agent may be used alone or in combination of two or more types. When two or more base generating agents are used in combination in the developer, it is preferable that their total content be within the range described above.

[0043] The developing solution may contain other components as well. Other components include, for example, known surfactants and known defoaming agents.

[0044] [Method of supplying developing solution] There are no particular restrictions on the method of supplying the developer, as long as the desired pattern can be formed. These methods include immersing the substrate on which the film has been formed in the developer, paddle development where the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred. Alternatively, the process may involve continuously supplying the developer solution through a straight nozzle, spinning the substrate to remove the developer solution from the substrate, spin-drying, and then continuously supplying the developer solution again through a straight nozzle, spinning the substrate to remove the developer solution from the substrate. This process may be repeated multiple times. Furthermore, possible methods for supplying the developer during the developing process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a nearly stationary state on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0045] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0046] <Processing steps> The method for producing the cured product of the present invention preferably includes a processing step between the developing step and the heating step in which a processing solution containing at least one compound selected from the group consisting of bases and base generators is brought into contact with the pattern, and more preferably includes a processing step between the developing step and the heating step in which a processing solution containing a base is brought into contact with the pattern. In this embodiment, it is believed that at least one compound selected from the group consisting of bases and base generators contained in the processing solution penetrates into the pattern after development. As a result, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin after the heating process is increased, and it is believed that the adhesion between the metal and the cured product is improved even when heated at a low temperature of 180°C or below.

[0047] The above processing step is preferably a rinsing step in which the above pattern is washed with the above processing liquid. Furthermore, the treatment solution is preferably a rinsing solution. Furthermore, it is preferable that the processing liquid is a rinsing liquid, and that the processing step is a rinsing step in which the pattern is washed with the rinsing liquid. In other words, the above processing step is preferably a rinsing step in which the pattern (the pattern obtained in the developing step) is washed with a rinsing solution containing at least one compound selected from the group consisting of bases and base generators. Furthermore, the above processing steps may be performed, for example, after the "other rinsing steps" described later.

[0048] [Processing liquid] The water content relative to the total mass of the treatment liquid is preferably 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less. The lower limit of the water content is not particularly limited and may be 0% by mass.

[0049] As the processing solution, for example, a solvent different from the solvent contained in the developer (for example, an organic solvent different from the organic solvent contained in the developer) can be used, and which contains at least one compound selected from the group consisting of bases and base generators.

[0050] -base- If the treatment solution contains a base, the boiling point of the base in the treatment solution at atmospheric pressure (101,325 Pa) is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 180°C or lower. The lower limit of the boiling point is not particularly limited, but if the treatment solution contains an organic solvent, it is preferably higher than the boiling point of the organic solvent (or the lowest boiling point among multiple organic solvents if the treatment solution contains multiple types) minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the treatment solution. For example, if the boiling point of the organic solvent is 100°C, the base used is preferably one with a boiling point of 80°C or higher, and more preferably one with a boiling point of 100°C or higher. Furthermore, preferred embodiments of the base contained in the processing solution are the same as preferred embodiments of the base contained in the developing solution described above.

[0051] If the treatment solution contains a base, the base content relative to the total mass of the treatment solution is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. Furthermore, if the base is not a liquid at 10 to 30°C, the base content is preferably 0.3 to 30% by mass, and more preferably 0.5 to 20% by mass. A single base may be used, or two or more bases may be used in combination. When two or more bases are used in combination in the treatment solution, it is preferable that their total content be within the range described above.

[0052] -Base Generator- The treatment solution may contain a base-generating agent. Examples of base generators include photobase generators and thermal base generators, with thermal base generators being preferred. As the above-mentioned photobase generator or thermobase generator, for example, any photobase generator or thermobase generator described later as a component included in the resin composition can be used without particular limitation.

[0053] If the treatment solution contains a base generating agent, the amount of base generating agent relative to the total mass of the treatment solution is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass, and even more preferably 0.08 to 5% by mass. The base generating agent may be used alone or in combination of two or more types. When two or more base generating agents are used in combination in the treatment solution, it is preferable that their total content be within the range described above.

[0054] The organic solvents contained in the treatment solution include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., alkyloxyacetate methyl, alkyloxyacetate ethyl acetate, alkyloxyacetate butyl (e.g., methoxyacetate methyl, methoxyacetate ethyl, methoxyacetate butyl, ethoxyacetate methyl, ethoxyacetate ethyl) 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ether Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as toluene, xylene, anisole, and other aromatic hydrocarbons, cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide. Furthermore, if the aforementioned base (for example, an organic base) is a liquid in the environment in which the processing solution is used, the aforementioned base can be used as both a solvent and a base.

[0055] If the treatment solution contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0056] When the treatment solution contains an organic solvent, it is preferable that 50% by mass or more of the total mass of the treatment solution be the organic solvent, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Alternatively, the treatment solution may be 100% by mass of the organic solvent.

[0057] The processing solution may also contain other components. Other components include, for example, known surfactants and known defoaming agents.

[0058] [Method of supplying the processing liquid] The method of supplying the processing solution is not particularly limited as long as the processing solution can be brought into contact with the pattern obtained in the developing process, but one example is supplying the processing solution onto the pattern obtained in the developing process. The above supply method is not particularly limited and includes methods such as immersing the substrate in the processing solution, supplying by paddle (liquid leveling) on ​​the substrate, supplying the processing solution to the substrate with a shower, and continuously supplying the processing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the processing liquid into the image area and manufacturing efficiency, there are methods for supplying the processing liquid using shower nozzles, straight nozzles, spray nozzles, etc., and a method of continuous supply using nozzles is preferred, and from the viewpoint of the penetration of the processing liquid into the image area, a method in which the processing liquid supplied by the nozzle is kept on the substrate is more preferred. The above methods for supplying the treatment solution (for example, a combination of supplying by a paddle and supplying by a shower, or supplying by a paddle and supplying by a straight nozzle) may be used in combination. For example, paddle supply has the effect of swelling the membrane, which makes it easier for the subsequent treatment solution to penetrate. Also, the treatment solution only needs to be used in at least one of the combined methods. Herein, in the present invention, the treatment process with the treatment solution may be carried out after supplying a treatment solution that does not contain a base and a base generating agent (for example, the rinsing solution in the other rinsing process described later) onto the pattern (for example, after supplying the rinsing solution onto the pattern and cleaning the pattern in the other rinsing process described later). The preferred embodiment of the treatment solution that does not contain a base and a base generating agent is the same as the preferred embodiment of the rinsing solution in the other rinsing process described later. The method for supplying the treatment solution, which does not contain a base or base generator, onto the pattern in the above embodiment is not particularly limited, but one example is supply by paddle. The method for supplying the processing liquid onto the pattern in the above embodiment is not particularly limited, but preferred methods include supply by shower or supply by straight nozzle. By supplying a base-free processing solution via a paddle, the pattern swells, making it easier for at least one compound selected from the group consisting of bases and base generators in the subsequently supplied processing solution to penetrate the pattern, thus making it easier to obtain effects such as improved elongation at break. Furthermore, supplying the processing solution via a shower, straight nozzle, etc., may also result in superior removal of developing residue (rinsing properties). Furthermore, possible methods for supplying the processing liquid during the processing step include a process in which the processing liquid is continuously supplied to the substrate, a process in which the processing liquid is kept in a nearly stationary state on the substrate, a process in which the processing liquid is vibrated on the substrate using ultrasound or the like, and a process that combines these methods. Among these, the processing step is preferably a step in which the processing solution is supplied to the developed pattern by showering or continuously supplying it. Furthermore, it is preferable to perform development in the development process by paddle development, and to supply the processing solution in the processing process at least once by shower or continuous supply using a straight nozzle or the like. According to the above embodiment, it is thought that the swelling of the pattern by paddle development makes it easier for at least one compound selected from the group consisting of bases and base generators in the processing solution to penetrate the pattern, thereby making it easier to obtain effects such as improved elongation at break.

[0059] The processing time in the processing step (i.e., the time the processing liquid is in contact with the pattern) is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the processing liquid during the processing step is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0060] <Other rinsing steps> The method for producing the cured product of the present invention may include a rinsing step (hereinafter also referred to as "another rinsing step") in which the above pattern (the pattern obtained in the developing step) is washed with a rinsing solution that does not contain either a base or a base generator. The method for producing the cured product of the present invention may include other rinsing steps, for example, before the processing step described above and after the developing step described above. Furthermore, if the method for producing the cured product of the present invention does not include the processing step described above, it may include the rinsing step after the developing step described above and before the heating step described above. As the rinsing solution in other rinsing steps, the same liquid as the treatment solution described above can be used, except that it does not contain a base and a base generating agent. The preferred embodiments of each component contained in the rinsing solution are the same as the preferred embodiments of each component other than the base and base generating agent contained in the treatment solution described above. Furthermore, the rinsing solution can be supplied to the pattern in the same manner as the processing solution described above.

[0061] <Post-development exposure process> The pattern obtained in the development process (or the pattern after rinsing, if a rinsing process is performed) may be subjected to a post-development exposure process in addition to the heating process described above, in which the pattern after the development process is exposed. In other words, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure process, for example, reactions such as the cyclization of polyimide precursors, etc., by exposure to a photobase generator, and the elimination of acid-degradable groups by exposure to a photoacid generator can be accelerated. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The exposure amount in the post-development exposure step is 50 to 20,000 mJ / cm², converted to exposure energy at the wavelength to which the photosensitive compound is sensitive. 2 Preferably, the concentration is 100 to 15,000 mJ / cm². 2 It is preferable that it be so. The post-development exposure step can be performed, for example, using the light source from the exposure step described above, and it is preferable to use broadband light.

[0062] <Metal layer formation process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. In other words, the method for producing a cured product of the present invention preferably includes a metal layer formation step in which a metal layer is formed on a pattern obtained by a developing step (preferably one that has been subjected to a heating step and at least one of a post-development exposure step).

[0063] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0064] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0065] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0066] <Physical properties of hardened material> [Mass reduction rate] In the method for producing a cured product of the present invention, when the film after the heating step is heated from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then heated from 260°C to 300°C at a rate of 10°C / min, the mass loss rate represented by formula A is 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less. The mass loss rate is measured by the method described in the examples below.

[0067] [Cyclization rate] In the method for producing a cured product of the present invention, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the resulting cured product is 95% or more, preferably 98% or more, and more preferably 99% or more. The upper limit of the above cyclization rate is not particularly limited and may be 100%. The above cyclization rate is calculated by the following method. If the precursor of the cyclized resin is a polyimide precursor or polyamideimide precursor, measure the infrared absorption spectrum of the film after the heating process and identify the absorption peak at 1377 cm⁻¹, which is derived from the imide structure. -1 The peak intensity P1 in the vicinity is determined. Next, the film after the heating process is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again, at 1377 cm⁻¹. -1 Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the cyclization rate (imidization rate) can be calculated based on the following formula. Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100 When the precursor of the cyclized resin is a polybenzoxazole precursor, the absorption peak at 1650 cm² is derived from the amide structure of the film after the heating step. -1 Determine the peak intensity Q1 in the vicinity. Next, 1490 cm -1 The absorption intensity of aromatic rings observed in the vicinity is used for normalization. Next, the film after the above heating process is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again, and the 1650 cm⁻¹ value is measured. -1 The peak intensity Q2 in the vicinity was calculated to be 1490 cm. -1The absorption intensity of aromatic rings observed in the vicinity is used for normalization. Using the normalized values ​​of the obtained peak intensities Q1 and Q2, the cyclization rate (oxazole rate) can be determined based on the following formula. Oxazole conversion rate (%) = (Specific value of peak intensity Q1 / Specific value of peak intensity Q2) × 100 Furthermore, in the measurement of the above cyclization rate (imidization rate, oxazole rate), 1377 cm³ was found in the composition. -1 Alternatively, 1377cm -1 , or 1490cm -1 Alternatively, 1650cm -1 If the sample contains compounds that absorb at a specific wavelength (e.g., phthalimide), the peak intensity derived from these compounds should be removed as background noise.

[0068] [Form, etc.] The form of the cured resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, by pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing heat dissipation functions. The thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. Furthermore, the shrinkage rate of the film before and after the heating process is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after the heating process, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (Volume after heating process ÷ Volume before heating process) × 100

[0069] The elongation at break of the cured product is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. There is no particular upper limit to the elongation at break, but for example, it should be 200% or less. The elongation at break can be measured in accordance with JIS (Japanese Industrial Standards) K 6251:2017. The glass transition temperature (Tg) of the cured product is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher. The upper limit of the glass transition temperature is not particularly limited, but for example, it may be 600°C or lower. The glass transition temperature can be measured in accordance with JIS K 7121:2012.

[0070] <Application> Examples of applications for the cured product manufacturing method of the present invention, or for the cured product of the present invention, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), or insulating films for the above-mentioned mounting applications. For these applications, see, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimides: Fundamentals and Applications," NTS, August 2010.

[0071] Furthermore, the method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used in the manufacture of printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for the manufacture of protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0072] (Resin composition) The resin compositions used in the method for producing the cured product of the present invention will be described below.

[0073] <Specific resin> The resin composition in the present invention contains a precursor of a cyclized resin (a specific resin). The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. In this invention, the main chain refers to the relatively longest bonding chain within the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. In other words, the resin composition in the present invention preferably contains, as a specific resin, at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. The resin composition in the present invention preferably contains a polyimide precursor as a specific resin. Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. When a specific resin has radical polymerizable groups, the resin composition in the present invention preferably contains a radical polymerization initiator as described below, and more preferably contains a radical polymerization initiator as described below and a radical crosslinking agent as described below. Furthermore, it may optionally contain a sensitizer as described below. A negative-type photosensitive film can be formed from such a resin composition in the present invention, for example. Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups. When a specific resin has an acid-degradable group, the resin composition in the present invention preferably contains a photoacid generator as described later. From such a resin composition in the present invention, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0074] [Polyimide precursor] The polyimide precursor used in this invention is not particularly limited in type, but it is preferable that it contains repeating units represented by the following formula (2). [ka] In formula (2), A 1 and A 2 Each of these independently comprises an oxygen atom or -NR z - represents R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0075] A in equation (2) 1 and A 2 Each of these independently comprises an oxygen atom or -NR Z - represents an oxygen atom, which is preferable. R z R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. z When R represents a monovalent organic group, Z A preferred embodiment is Z in equation (3-1) described later. 1 This is similar to the preferred embodiment. R in equation (2) 111-Ar- and -Ar-L-Ar- are examples of divalent organic groups. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of 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 combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and aromatic group, the hydrocarbon group of the ring member may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and 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-, -SO2- or -NHCO-, or a group consisting of two or more of the above. The preferred ranges for these are as described above.

[0076] R 111 It is preferable that the polyimide precursor is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One type of diamine may be used, or two or more types may be used. Specifically, the diamine 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 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 hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0077] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-; and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0078] Diamines specifically 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 isophoronediamines; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-Bis(4-aminophenyl)-10-Hydroanthracene, 3,3',4,4'-Tetraaminobiphenyl, 3,3',4,4'-Tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- 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, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,Examples include at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0079] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0080] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0081] R 111 From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0082] Also, R 111From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0083] Furthermore, from the viewpoint of moisture resistance and chemical resistance of the resulting cured product, R 111 It is preferable that it contains a group represented by any of the following formulas (5) to (7), and more preferably a group represented by any of the following formulas (5) to (7). Among these, from the viewpoint of suppressing film shrinkage during curing, R 111 Preferably, the group is represented by the following formula (5). [ka] In formulas (5) to (7), Y 1 represents a single bond or a divalent linking group, Y 2 The symbols represent single or divalent linking groups, and * represents a bonding site with another structure.

[0084] In formula (5), Y 1 These are single bonds or aliphatic hydrocarbon groups having 1 to 10 carbon atoms, which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NR N - or a group selected from a combination thereof is preferred, and a single bond or an isopropylidene group is more preferred. N Each of these independently represents a hydrogen atom or a hydrocarbon group, with a hydrogen atom, an alkyl group, or an aryl group being more preferred, a hydrogen atom or an alkyl group being even more preferred, and a hydrogen atom being particularly preferred.

[0085] In formula (6), Y 2 These are single bonds or aliphatic hydrocarbon groups having 1 to 10 carbon atoms, which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NR N - or a group selected from a combination thereof, and a single bond or -O- is more preferred. N As stated above.

[0086] The group represented by formula (7) is preferably the group represented by formula (7-1) below. [ka]

[0087] From the perspective of suppressing curing shrinkage, among these, R 111 It is preferable that it contains a group represented by the following formula (4), and more preferably that it is a group represented by formula (4). [Chemical formula] In formula (4), * each represents a bonding site with another structure.

[0088] R in formula (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [[ID=__15]][Chemical formula] In formula (5), R 112 is a single bond or a divalent linking group, and is preferably a group selected from a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, and -NHCO-, and combinations thereof. More preferably, it is a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- and -SO2-. Even more preferably, it is a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0089] R 115 specifically includes, for example, a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. The polyimide precursor may contain only one kind or two or more kinds of structures corresponding to R 115 as a tetracarboxylic dianhydride residue. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [[ID=__34]][Chemical formula] In formula (O), R 115 represents a tetravalent organic group. The preferable range of R 115 is synonymous with R 115 in formula (2), and the preferable range is also the same.

[0090] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, and 2,2 ',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, Examples include 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of these having 1 to 6 carbon atoms.

[0091] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0092] In equation (2), R 111 and R115 It is also possible that at least one of them has an OH group. More specifically, R 111 Examples include residues of bisaminophenol derivatives.

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

[0094] [ka]

[0095] In equation (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In equation (III), * represents a bonding site with another structure. In equation (III), R 201 This represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxy group. Suitable R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. As the polyalkyleneoxy group, from the viewpoints of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group formed by bonding the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may form blocks and be arranged, or may be arranged in a pattern such as alternating. The preferable embodiments of the repeating number of the ethyleneoxy group and the like in these groups are as described above.

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

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

[0098] Further, it is also preferable that the polyimide precursor has a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0099] Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, there are exemplified modes such as using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0100] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude. Formula (2-A)

Chemical formula

[0102] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0103] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0104] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of molecular weight dispersion is the value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, if the resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0105] [Polybenzoxazole precursor] The polybenzoxazole precursor used in this invention does not have any particular structure, but preferably contains repeating units represented by the following formula (3). [ka] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0106] In equation (3), R 123 and R 124 These are R in equation (2), respectively. 113 This is synonymous with the same, and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group. In equation (3), R 121 R represents a divalent organic group. A divalent organic group is preferably one containing at least one of an aliphatic group and an aromatic group. A linear aliphatic group is preferred. 121 A dicarboxylic acid residue is preferred. One or more dicarboxylic acid residues may be used.

[0107] As the dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, and dicarboxylic acid residues containing an aromatic group are more preferred. As for dicarboxylic acids containing an aliphatic group, dicarboxylic acids containing a linear or branched (preferably linear) aliphatic group are preferred, and dicarboxylic acids consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. Examples include suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formula.

[0108] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0109] As for dicarboxylic acids containing aromatic groups, dicarboxylic acids having the following aromatic groups are preferred, and dicarboxylic acids consisting only of the following aromatic groups and two -COOH groups are more preferred.

[0110] [ka] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-, and * represents a binding site with another structure, independently.

[0111] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0112] In equation (3), R 122 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) above is 115 This is synonymous with the same thing, and the preferred range is also similar. R 122It is also preferable that the group is derived from a bisaminophenol derivative, and examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(4-amino Examples include bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used individually or in combination.

[0113] Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

[0114] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Also, R 122 It is also preferable that the structure be represented by the above formula. 122However, if the structure is represented by the above formula, then of the four * and # characters, any two of them are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the other two are R in formula (3). 122 It is preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 Either the bond site with the nitrogen atom to which it is bonded, or the two *s are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the two #s are R in formula (3). 122 It is more preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 It is even more preferable that the site is a bonding site with the nitrogen atom to which it is bonded.

[0115] The bisaminophenol derivative is also preferably a compound represented by formula (As). [ka]

[0116] In formula (As), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of formulas (A-sc) below. R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

[0117] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

[0118] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, is considered to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, and is particularly preferable because it further enhances the effect of high cyclization rate when cured at low temperatures.

[0119] Furthermore, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, as this maintains the effects of high transparency to i-lines and a high cyclization rate when cured at low temperatures.

[0120] Furthermore, it is even more preferable that R1 in the above formula (As) is an alkylene or a substituted alkylene. Specific examples of alkylenes and substituted alkylenes for R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferable because they allow for the production of a well-balanced polybenzoxazole precursor that maintains high transparency to i-lines and a high cyclization rate when cured at low temperatures, while also having sufficient solubility in solvents.

[0121] For a method of producing the bisaminophenol derivative represented by the above formula (As), refer to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference.

[0122] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated herein by reference. Of course, it goes without saying that we are not limited to these.

[0123] The polybenzoxazole precursor may include other types of repeating units in addition to the repeating unit of formula (3) above. The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that it can suppress the occurrence of warping associated with ring closure.

[0124] [ka] In equation (SL), Z has an a structure and a b structure, and R 1s R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 2s R is a hydrocarbon group having 1 to 10 carbon atoms. 3s , R 4s , R 5s , R 6s At least one of the groups is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of structures a and b may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol% for structure a, 95 to 5 mol% for structure b, and 100 mol% for a + b.

[0125] In formula (SL), preferred Z is R in the b structure. 5s and R 6s Examples include those in which the group is a phenyl group. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, thereby achieving both the effect of suppressing warping and the effect of improving solvent solubility.

[0126] When other types of repeating units include diamine residues represented by formula (SL), it is also preferable to include tetracarboxylic acid residues remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as repeating units. An example of such tetracarboxylic acid residues is R in formula (2). 115 Examples include:

[0127] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The degree of molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole precursor, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazole precursors are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polybenzoxazole precursors as a single resin are, respectively, within the above range.

[0128] [Polyamide-imide precursor] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 is an oxygen atom or -NR z - represents R 113 R represents a hydrogen atom or a monovalent organic group. z represents a hydrogen atom or a monovalent organic group.

[0129] In formula (PAI-2), R 117Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0130] Also, R 117It is preferable that it be derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. Chlorination is preferred as the halogenation. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the above tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used individually or in combination of two or more.

[0131] Specifically, preferred tricarboxylic acid compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0132] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene group. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group has been converted to a halogen (e.g., trimellitic anhydride chloride).

[0133] In formula (PAI-2), R 111 , A 2 , R113 , R z These are the R values ​​in equation (2) above. 111 , A 2 , R 113 , R z This is synonymous with the same as the preferred configuration.

[0134] The polyamide-imide precursor may further contain other repeating units. Other repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below. [ka]

[0135] In formula (PAI-1), R 116 represents a divalent organic group, R 111 This represents a divalent organic group. In formula (PAI-1), R 116 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0136] Also, R 116 It is preferable that it be derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl group in a dicarboxylic acid dihalide compound may be halogenated, but it is preferable that it is chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used individually or in combination of two or more.

[0137] Specifically, preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0138] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebaic acid, and hexadeca. Examples include fluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalide compounds include compounds in which the two carboxyl groups in the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

[0139] In formula (PAI-1), R 111 R in equation (2) above is 111 This is synonymous with the same as the preferred configuration.

[0140] Furthermore, it is preferable that the polyamide-imide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0141] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine component.

[0142] One embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be any of the repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2). Another embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0143] The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyamide-imide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyamide-imide precursors as a single resin are, respectively, within the above ranges.

[0144] Furthermore, among these, it is preferable that the specific resin includes a resin having at least one of the repeating units represented by formula (1-1) and the repeating units represented by formula (1-2). Here, the repeating unit represented by equation (1-1) is a preferred embodiment of the repeating unit represented by equation (2) above, and the repeating unit represented by equation (1-2) is a preferred embodiment of the repeating unit represented by equation (PAI-2) above. [ka] In equation (1-1) or equation (1-2), W 1 represents a divalent organic group, X 1 represents a tetravalent organic group, R 1 ~R 3 Each of these independently represents a group represented by formula (3-1) or a group represented by formula (3-2) below, W 2 represents a divalent organic group, X 2 represents a trivalent organic group, and the resin is a repeating unit represented by formula (1-1), R 1 and R 2 A repeating unit in which at least one of is a base represented by formula (3-1), and a repeating unit represented by formula (1-2) R 3 It includes at least one repeating unit selected from the group of repeating units whose base is represented by equation (3-1). [ka] In formula (3-1) and formula (3-2), Z 1 and Z 2 Each of these independently represents an organic group, Z 1 and Z 2 They may bond to form a ring structure, A 2 represents an oxygen atom or -NH-, R 113 * represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. Also, in equation (1-1), R 1 and R 2 If both are groups represented by formula (3-1), then R 1 and R 2 Each of these groups must correspond to a group represented by formula (3-1), and R 1 and R 2 These may be the same group or different groups. In equation (1-1), R 1 and R 2 If both are groups represented by formula (3-2), then R 1 and R 2 Each of these must be a group that corresponds to the group represented by formula (3-2), and R 1 and R 2 These may be the same group or different groups.

[0145] According to this embodiment, a base is generated from the structure represented by formula (3-1) by cyclization (ring closure) of the specific resin, and ring closure is further promoted. Therefore, even if the cured product is obtained by heating at a low temperature of 180°C or below, it is thought that a cured product with excellent adhesion to metal can be obtained. Furthermore, for example, when using a base generator as described later, residues of the base generator after base generation may remain in the cured product. However, if the resin has at least one of the repeating units represented by formula (1-1) and formula (1-2), the remaining material is the ring-closed resin. Therefore, it is thought that the residue of low-molecular-weight compounds in the film after the heating process is eliminated, and adhesion to the metal is further improved.

[0146] When the specific resin has at least one of the repeating units represented by formula (1-1) and the repeating units represented by formula (1-2), it is preferable that the specific resin generates a base at a temperature of 120 to 180°C. Furthermore, it is preferable that the specific resin generates a base during the heating process described above. Whether or not a particular resin generates a base at a certain temperature X°C is determined by the following method. After heating 1 mole of a specific resin in a sealed container at 1 atmosphere at the above-mentioned X°C for 3 hours, the amount of decomposition can be quantified by methods such as HPLC (high-performance liquid chromatography) to determine whether or not a base is generated. The amount of base generated is preferably 0.1 moles or more, and more preferably 0.5 moles or more. There is no particular upper limit to the amount of base generated, but it can be, for example, 1000 moles or less.

[0147] The molecular weight of the base generated from the specific resin is preferably 40 to 1,000, more preferably 40 to 500, and even more preferably 50 to 400. The boiling point of the base having the pyridine structure described above at 1 atmosphere is preferably 50 to 600°C, more preferably 50 to 500°C, and even more preferably 50 to 450°C.

[0148] The generated base is preferably a base whose conjugate acid has a pKa of 0 or greater, more preferably a base with a pKa of 3 or greater, and even more preferably a base with a pKa of 6 or greater. The upper limit of the pKa of the conjugate acid is not particularly limited, but it is preferably 30 or less. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​are calculated using ACD / ChemSketch®. If there are multiple pKa values ​​for the above-mentioned conjugate acids, it is preferable that at least one of them falls within the above range.

[0149] In formula (1-1), X 1 R in equation (2) 115 This is synonymous with the same as the preferred configuration. In formula (1-1), W 1 R in equation (2) 111 This is synonymous with the same as the preferred configuration.

[0150] In formula (3-1), Z 1 and Z 2 Each of these independently represents an organic group, a hydrocarbon group, or a hydrocarbon group with -O-, -C(=O)-, -S-, -S(=O)2-, and -NR N A group represented by a combination of at least one group selected from the group consisting of - is preferred, and a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -O- is preferred. N As stated above. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The number of carbon atoms in the above aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Furthermore, the above-mentioned aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, or a structure represented by a combination of these. The number of carbon atoms in the above aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. The above hydrocarbon group may have known substituents within the range in which the effects of the present invention can be obtained.

[0151] Also, Z 1 and Z 2 An embodiment in which at least one of the members has a polymerizable group is also one of the preferred embodiments of the present invention. Examples of polymerizable groups include radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radical polymerizable groups being preferred. Preferred radical polymerizable groups are those having an ethylenically unsaturated group, such as (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, styryl group, vinyl group, and (meth)allyl group. Among these, the (meth)acryloxy group is preferred from the viewpoint of reactivity. These polymerizable groups may be directly bonded to the nitrogen atom in formula (3-1), or they may be bonded via linking groups such as hydrocarbon groups (e.g., alkylene groups).

[0152] Also, in equation (3-1), Z 1 and Z 2 They may combine to form a ring structure. The resulting ring structure may be an aromatic ring structure or an aliphatic ring structure, but an aliphatic ring structure is preferred, and a saturated aliphatic ring structure is more preferred. The above ring structure is preferably a cyclic amine having 2 to 10 carbon atoms, such as a pyrrolidine ring, piperidine ring, morpholine ring, octahydroindole ring, octahydroisoindole ring, pyrrole ring, or pyridine ring, with pyrrolidine ring, piperidine ring, or morpholine ring being preferred. Furthermore, the above-mentioned ring structure may have substituents to the extent that the effects of the present invention can be obtained. Examples of substituents include hydrocarbon groups and halogen atoms. Examples of ring structures substituted with substituents include dimethylpiperidine rings.

[0153] The group represented by formula (3-1) is preferably the group represented by formula (3-1-1) or formula (3-1-2) below. [ka] In formula (3-1-1), Cy represents an aliphatic ring structure or an aromatic ring structure, and * represents a bonding site with other structures. In formula (3-1-2), Z 3 and Z 4 Each of these independently represents an alkyl group, and * represents a bonding site with other structures.

[0154] In formula (3-1-1), the ring structure represented by Cy is preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure. Examples of the ring structure represented by Cy include a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydroindole ring, an octahydroisoindole ring, a pyrrole ring, and a pyridine ring, with a pyrrolidine ring, a piperidine ring, or a morpholine ring being preferred. Furthermore, the ring structure represented by Cy above may have substituents to the extent that the effects of the present invention can be obtained. Examples of substituents include hydrocarbon groups and halogen atoms. Examples of ring structures substituted with substituents include dimethylpiperidine rings.

[0155] In formula (3-1-2), Z 3 and Z 4Each of these independently represents an alkyl group, with alkyl groups having 1 to 20 carbon atoms being preferred, alkyl groups having 1 to 10 carbon atoms being more preferred, and alkyl groups having 1 to 8 carbon atoms being even more preferred. The alkyl group described above may have a linear, branched, or cyclic structure, or a combination thereof.

[0156] The following are some specific examples of the base represented by equation (3-1), but they are not limited to these. [ka]

[0157] In formula (3-2), A 2 An oxygen atom is preferred. In formula (3-2), R 113 R in equation (2) 113 This is synonymous with the same as the preferred configuration.

[0158] If the specified resin contains repeating units represented by formula (1-1), the specified resin may further contain other repeating units. In the case where the specific resin contains repeating units represented by formula (1-1), one preferred embodiment of the present invention is that the content of repeating units represented by formula (1-1) relative to the total repeating units contained in the specific resin is 50 mol% or more. Furthermore, the above content is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more. The above content limit is not particularly limited and may be 100 mol%.

[0159] In formula (1-2), W 2 and R 3 These are W in equation (1-1), respectively. 1 and R 2 This is synonymous with the same as the preferred configuration. In formula (1-2), X 2 R in the above equation (PAI-2) is117 This is synonymous with the same as the preferred configuration. If the specified resin contains repeating units represented by formula (1-2), the specified resin may further contain other repeating units. Other repeating units include the repeating unit represented by equation (1-1) above, the repeating unit represented by equation (PAI-1) above, and so on.

[0160] In the case where the specific resin contains repeating units represented by formula (1-2), an embodiment in which the content of repeating units represented by formula (1-2), repeating units represented by formula (1-1), and repeating units represented by formula (PAI-1) is 50 mol% or more relative to the total repeating units contained in the specific resin is also one of the preferred embodiments of the present invention. Furthermore, the above content is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more. Furthermore, in the case where the specific resin contains repeating units represented by formula (1-2), an embodiment in which the content of repeating units represented by formula (1-2) relative to the total repeating units contained in the specific resin is 50 mol% or more is also one of the preferred embodiments of the present invention. Furthermore, the above content is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more. The above content limit is not particularly limited and may be 100 mol%.

[0161] The ratio of the total molar amount of the group represented by formula (3-1) to the total molar amount of the group represented by formula (3-2) contained in the specific resin is preferably 0.1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. The total molar amount of the group represented by (3-2) above, and the total molar amount of the group represented by formula (3-1), can be calculated, for example, by NMR (nuclear magnetic resonance spectrometer). Furthermore, for the purpose of improving chemical resistance and pattern formation, the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of the groups represented by formula (3-2) contained in the specific resin is preferably 99.9 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 80 mol% or less. Furthermore, in order to promote the cyclization of the polyimide precursor resin and the polyamideimide precursor resin, thereby lowering the heating temperature in the heating process and improving the elongation at break, it is preferable that the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of the groups represented by formula (3-2) contained in the specific resin be 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 98 mol% or more. An embodiment in which the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of the groups represented by formula (3-1) to the total molar amount of the groups represented by formula (3-2) contained in the specific resin is 100 mol% is also one of the preferred embodiments of the present invention.

[0162] Furthermore, the molar amount of the group represented by formula (3-1) contained in the specific resin relative to the total mass of the specific resin is preferably 0.001 to 10 mmol / g, more preferably 0.01 to 5 mmol / g, and even more preferably 0.1 to 3 mmol / g. Furthermore, the content of the group represented by formula (3-1) in the specific resin relative to the total mass of the specific resin is preferably 0.1 to 70%, more preferably 0.5 to 40%, and even more preferably 1 to 20%.

[0163] [Method for producing polyimide precursors, etc.] Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0164] -End-capturing agent- In the production method of polyimide precursors, etc., it is preferable to encapsulate the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When encapsulating the carboxylic acid anhydride and acid anhydride derivative remaining at the resin ends, examples of end encapsulants include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and from the standpoint of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferable. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenolic compounds.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants. Furthermore, when sealing the amino groups at the ends of the resin, it is possible to seal them with compounds having functional groups that can react with the amino groups. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0165] Furthermore, a compound represented by formula (T-1) may be used as an end-capturing agent. By encapsulating the ends with such a compound, a structure that readily generates bases at the ends can be introduced, and it is believed that the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin tends to increase even when cured at low temperatures. [ka] In formula (T-1), L T represents a divalent organic group, Z 1 and Z 2 Each of these independently represents an organic group, Z 1 and Z 2 They may be bonded together to form a ring structure.

[0166] In formula (T-1), L T It is preferably a hydrocarbon group, and may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably an aromatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group. L TLinked chain length in (i.e., L T The minimum number of atoms connecting the two carbonyl groups bonded to each other is preferably 2 to 4, and more preferably 2. In formula (T-1), Z 1 and Z 2 This is Z in equation (3-1). 1 and Z 2 This is synonymous with the same as the preferred configuration. In particular, Z 1 and Z 2 An embodiment in which at least one of the members has a polymerizable group is also one of the preferred embodiments of the present invention. Examples of polymerizable groups include radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radical polymerizable groups being preferred. Preferred radical polymerizable groups are those having an ethylenically unsaturated group, such as (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, styryl group, vinyl group, and (meth)allyl group. Among these, the (meth)acryloxy group is preferred from the viewpoint of reactivity. These polymerizable groups may be directly bonded to the nitrogen atom in formula (T-1), or they may be bonded via linking groups such as hydrocarbon groups (e.g., alkylene groups).

[0167] Specific examples of compounds represented by formula (T-1) include, but are not limited to, the following compounds. [ka]

[0168] -Solid precipitation- The production of polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. The resulting solid is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the process may include a step for removing ionic impurities using an ion exchange resin.

[0169] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more, based on the total solid content of the resin composition. Herein, from the viewpoint of adhesion of the cured product to metal, one preferred embodiment of the present invention is that the resin composition contains a solvent and the content of the cyclized resin precursor is 70% by mass or more relative to the total solid content of the resin composition. Furthermore, the resin content in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition in the present invention may contain only one specific resin or two or more specific resins. When two or more specific resins are included, it is preferable that the total amount is within the above range.

[0170] Furthermore, the resin composition in the present invention preferably contains at least two types of resins. Specifically, the resin composition in the present invention may contain a total of two or more specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition in the present invention contains two or more specific resins, for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above). 115 Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0171] <Other resins> The resin composition in the present invention may include the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a polymerizable compound with a high polymerizable value of 20,000 or less weight-average molecular weight (for example, the molar amount of polymerizable groups in 1g of resin is 1 × 10⁻⁶) -3 By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0172] If the resin composition in the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition in the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0173] <Polymerizable compound> The resin composition in the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0174] The resin composition in the present invention preferably contains a polymerizable compound having a boiling point of 270°C or higher at 1 atmosphere. Furthermore, the upper limit of the boiling point is not particularly limited; for example, it can be 500°C or lower. According to the above embodiment, the above-mentioned mass reduction rate can be reduced.

[0175] The polymerizable compound having a boiling point of 270°C or higher at 1 atmosphere is preferably a compound having three or more polymerizable groups, more preferably a compound having four or more polymerizable groups, and even more preferably a compound having five or more polymerizable groups. The upper limit of the number of polymerizable groups is not particularly limited, but it is preferably 20 or less. Furthermore, the polymerizable compound having a boiling point of 270°C or higher at 1 atmosphere is preferably a compound having three or more (meth)acrylate groups, more preferably a compound having four or more (meth)acrylate groups, and even more preferably a compound having five or more (meth)acrylate groups. The upper limit of the number of (meth)acrylate groups is not particularly limited, but it is preferably 20 or less.

[0176] Specific examples of polymerizable compounds having a boiling point of 270°C or higher at 1 atmosphere include dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, and ethoxylated dipentaerythritol polymethacrylate. Furthermore, these compounds, whether acrylates or methacrylates, can be used as long as their boiling point is 270°C or higher. These compounds may be commercially available products; for example, those manufactured by Shin-Nakamura Chemical Industry Co., Ltd. can be used.

[0177] [Radical Crosslinking Agent] The resin composition in the present invention preferably contains a radical crosslinking agent. Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups. Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0178] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition in the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

[0179] 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.

[0180] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0181] Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane, among others. Examples of polyfunctional acrylates and methacrylates, as well as mixtures thereof, include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated; urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193; polyester acrylates as described in Japanese Unexamined Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490; and epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid. Compounds described in paragraphs 0254 to 0257 of Japanese Unexamined Patent Publication No. 2008-292970 are also suitable. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond.

[0182] In addition, other preferred radical crosslinking agents besides those mentioned above include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent No. 4364216, etc., as well as cardo resins.

[0183] Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, as well as vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesion Society of Japan, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0184] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be preferably used, and these contents are incorporated herein.

[0185] Furthermore, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylateing them, as described in Japanese Patent Publication No. 10-062986 with specific examples of formulas (1) and (2), can also be used as radical crosslinking agents.

[0186] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Publication No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein by reference.

[0187] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin Nakamura Chemical Industry Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0188] Examples of commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethylene oxy chains, manufactured by Sartomer; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains, also manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxy chains; and urethane. Examples include oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0189] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0190] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0191] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing, as well as excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0192] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is approximately 200. In the present invention, from the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition. Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0193] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition in the present invention. 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.

[0194] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0195] [Other crosslinking agents] The resin composition in the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process. Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used. As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents. Among these, the resin composition in the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0196] Examples of compounds containing at least one alkoxymethyl group and acyloxymethyl group in the present invention include compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

[0197] [ka]

[0198] R 100 This represents an alkyl group or acyl group. R 101 and R 102 Each of these independently represents a monovalent organic group and may be bonded to each other to form a ring.

[0199] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted for an aromatic group include compounds with the following general formula.

[0200] [ka]

[0201] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103This includes hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or groups that decompose upon the action of an acid to produce alkali-soluble groups (for example, groups that are eliminated by the action of an acid, -C(R 4 ) 2COOR 5 The group represented by (R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 The symbol indicates a group that is removed by the action of an acid. R 105 Each independently represents an alkyl group or an alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Groups that decompose under the action of acid to produce alkali-soluble groups, groups that are eliminated under the action of acid, -C(R 4 ) 2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 Examples include: In the formula, R 36 ~R 39 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 These elements may be joined together to form a ring. The alkyl group described above is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group described above may be linear or branched. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those described above for preferred embodiments of alkyl and aryl groups. The above alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

[0202] R 01 and R 02 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0203] These groups are preferably tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups, etc. More preferably, they are tertiary alkyl ester groups and acetal ester groups.

[0204] The following structures are examples of compounds containing an alkoxymethyl group. Compounds containing an acyloxymethyl group are examples of compounds obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. The following compounds are examples of compounds containing an alkoxymethyl group or acyloxymethyl group in the molecule, but are not limited to these.

[0205] [ka]

[0206] [ka]

[0207] The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

[0208] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0209] Specific examples of urea-based crosslinking agents include, for example, glycoluryl crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Ethylene urea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea. Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea. Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0210] Specific examples of benzoguanamine crosslinking agents include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, Examples include dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0211] In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0212] Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. Examples include TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0213] Furthermore, the resin composition in the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0214] - Epoxy compounds (compounds containing epoxy groups) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition in the present invention.

[0215] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably with 2 to 15 repeating units.

[0216] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (all product names, manufactured by DIC Corporation), Licaresin® BEO-20E, Licaresin® BEO-60E, Licaresin® HBE-100, Licaresin® DME-100, Licaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples include 0-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

[0217] [ka]

[0218] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0219] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0220] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0221] -Benzoxazine compounds (compounds containing a benzoxazolyl group)- Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

[0222] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0223] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition in the present invention. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0224] The resin composition in the present invention preferably contains a photosensitive agent. Examples of photosensitive agents include photopolymerization initiators and photoacid generators, with photopolymerization initiators being preferred.

[0225] [Polymerization initiator] The resin composition in the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. It is particularly preferable that it contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that interacts with a photoexcited sensitizer to generate active radicals.

[0226] The photoradical polymerization initiator is present in a wavelength range of approximately 240-800 nm (preferably 330-500 nm) at a concentration of at least approximately 50 L·mol. -1 ·cm -1 It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0227] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165-0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

[0228] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0229] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0230] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0231] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0232] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, whose absorption maximum wavelength is matched to a light source of wavelengths such as 365 nm or 405 nm, can also be used, and this is incorporated herein by reference.

[0233] Examples of acylphosphine initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

[0234] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0235] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0236] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP 2004-534797 A, compounds described in JP 2006-342166 A, compounds described in JP 2017-019766 A, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in JP 2017-198865 A, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0237] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linking group in their molecule.

[0238] [ka]

[0239] Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arcules NCI-730, NCI-831, and ADEKA Arcules NCI-930 (manufactured by ADEKA Corporation). Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds with the following structures can also be used. [ka]

[0240] As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the details of which are incorporated herein by reference.

[0241] As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505, which are incorporated herein by reference.

[0242] Furthermore, oxime compounds containing a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Publication No. 2013-164471, the details of which are incorporated herein by reference.

[0243] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein by reference. Another example of an oxime compound having a nitro group is ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0244] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0245] As a photo-radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photo-polymerization initiators include the compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0246] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. OX1 An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. OX1 Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0247] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. R X2 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. R X3 ~R X14 Each of these independently represents a hydrogen atom or a substituent; However, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0248] In the above formula, R X12 R is an electron-withdrawing group, X10 , R X11 , R X13 , R X14 It is preferable that it is a hydrogen atom.

[0249] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, which are incorporated herein by reference.

[0250] The most preferred oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as described in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0251] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0252] Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, and the use of a metallocene compound or an oxime compound being even more preferred.

[0253] Furthermore, photoradical polymerization initiators can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones fused with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethylketal. In addition, compounds represented by the following formula (I) can also be used.

[0254] [ka]

[0255] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. I01 is a group represented by formula (II), or R I00 It is the same group as R I02 ~R I04 Each of these is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0256] [ka]

[0257] In the formula, R I05 ~R I07 This is R in equation (I) above. I02 ~R I04 It is the same as this.

[0258] Furthermore, the photoradical polymerization initiator may be a compound described in paragraphs 0048-0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0259] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1-7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0260] If a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition in the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range. Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[0261] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenones, Michlaz ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyranes, and indigos. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-Tolyldiethanolamine, N-phenylethanolamine, 4-Morpholinobenzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Examples include amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details regarding the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0262] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0263] [Chain transfer agent] The resin composition in the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0264] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0265] When the resin composition in the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition in the present invention. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total is within the above range.

[0266] <Base Generator> The resin composition in the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. The base-generating agent referred to herein does not include the specific resins mentioned above. Preferred base-generating agents for the resin composition in the present invention include thermal base-generating agents and photobase-generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages. The base generator can be either an ionic base generator or a non-ionic base generator. Examples of bases generated from base-generating agents include secondary amines and tertiary amines. There are no particular restrictions on the base-generating agent according to the present invention, and known base-generating agents can be used. Examples of known base-generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific examples of nonionic base-generating compounds include those represented by formulas (B1), (B2), or (B3). [ka]

[0267] In equations (B1) and (B2), Rb1 , Rb 2 and Rb 3 Each of these is independently an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb 1 and Rb 2 They cannot become hydrogen atoms at the same time. Also, Rb 1 , Rb 2 and Rb 3 None of these have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply when the bonded carbon atom forms a carbonyl group, i.e., when it forms an amide group together with the nitrogen atom.

[0268] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Preferably, at least one of these components contains a cyclic structure, and more preferably, at least two contain cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a 5-membered ring or a 6-membered ring, with a 6-membered ring being preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0269] More specifically, Rb 1 and Rb 2 The group is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that provides the effects of the present invention. Rb 1 and Rb 2These may be bonded to each other to form a ring. A preferred ring is a 4-7 member nitrogen-containing heterocycle. Rb 1 and Rb 2 In particular, it is preferable that the alkyl group is a linear, branched, or cyclic alkyl group which may have substituents (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have substituents (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a cyclohexyl group which may have substituents.

[0270] Rb 3 Examples include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb 3 It may further have substituents to the extent that it exhibits the effects of the present invention.

[0271] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2). [ka]

[0272] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 These are, respectively, Rb in equation (B1). 1 and Rb 2 It is the same as this. Rb 13 The group is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents within a range that provides the effects of the present invention. In particular, Rb 13 An aryl alkyl group is preferred.

[0273] Rb 33 and Rb 34 Each of these is independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably 1 to 8, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably 2 to 8, and still more preferably 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

[0274] Rb 35 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

[0275] Compounds represented by formula (B1-1) are preferred, as are compounds represented by formula (B1-1a). [ka]

[0276] Rb 11 and Rb 12 Rb in equation (B1-1) 11 and Rb 12 It is synonymous with [the above]. Rb 15 and Rb 16 The group is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and still more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and still more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and still more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and still more preferably with 7 to 11 carbon atoms), with a hydrogen atom or a methyl group being preferred. Rb 17 The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and still more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and still more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and still more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and still more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

[0277] [ka]

[0278] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen and carbon atoms, and having 3 or more atoms on the linking chain pathway. N1 and R N2 Each of these independently represents a monovalent organic group.

[0279] In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that links these linked objects in the shortest possible distance (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4. [ka]

[0280] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0281] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1). [ka]

[0282] In formula (N1), R N1 and R N2 Each of these independently represents a monovalent organic group, RC1 represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0283] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

[0284] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and is preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include an aliphatic hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), with an aliphatic hydrocarbon group being preferred. N1 and R N2 Using an aliphatic hydrocarbon group is preferable because it results in a base with high basicity. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and they may also have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0285] R N1 and R N2Examples of aliphatic hydrocarbon groups that constitute the linear alkyl group include linear or branched alkyl groups, cyclic alkyl groups, groups relating to a combination of linear alkyl groups and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched alkyl groups are preferably those having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, and the like. The cyclic alkyl group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. The group comprising the combination of a linear alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. Examples of groups comprising the combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. In particular, from the perspective of raising the boiling point of the decomposition product bases described later, R N1 and R N2 A C5-C12 alkyl group is preferred. However, in formulations where adhesion to a metal (e.g., copper) layer is important, a cyclic alkyl group or a C1-C8 alkyl group is preferred.

[0286] R N1 and R N2These may be linked together to form a cyclic structure. In forming a cyclic structure, oxygen atoms, etc., may be present in the chain. Also, R N1 and R N2 The cyclic structure formed may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1), and examples include a pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, and morpholine ring, with pyrroline ring, pyrrolidine ring, piperidine ring, and morpholine ring being preferred.

[0287] R C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

[0288] As a protecting group, a protecting group that decomposes upon the action of an acid or a base is preferred, and a protecting group that decomposes with an acid is particularly preferred.

[0289] Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methyloxymethyl (MOM) and ethyloxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0290] There are no specific requirements for the divalent linking group constituting L, but hydrocarbon groups are preferred, and aliphatic hydrocarbon groups are more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, it is preferable to have a divalent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, or a group which is a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylenealkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0291] The preferred linking group L is specifically a linear or branched linear alkylene group, a cyclic alkylene group, a group relating to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group. The linear or branched alkylene group is preferably composed of 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms. The combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

[0292] The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group is preferably one with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0293] Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

[0294] [ka]

[0295] 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.

[0296] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0297] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0298] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0299] When the resin composition in the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition in the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less. One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range. Furthermore, as described above, in the present invention, bases can also be generated from specific resins, or a base or base-generating agent can be included in the developing solution or processing solution and permeated into the film. Therefore, compared to conventional resin compositions containing base-generating agents and cyclized resins or their precursors, the base-generating agent content can be reduced. As a result, residues of the base-generating agent after base generation, as well as undecomposed base-generating agents themselves, are less likely to remain in the composition, which is expected to improve the adhesion to metal and moisture resistance of the cured product. In these embodiments, it is also preferable that the base generating agent content be 2% by mass or less per 100 parts by mass of resin. Furthermore, it is also preferable that the base generating agent content be 1% by mass or less per 100 parts by mass of resin, and more preferably 0.5% by mass or less. It is also preferable that the base generating agent content be 0.1% by mass or less per 100 parts by mass of resin. In these embodiments, the lower limit of the base generating agent content may be 0% by mass. The amount of base-generating agent can be determined by considering the type and amount of base generated from the specific resin, the type and amount of base contained in the developer or processing solution, heating conditions, etc.

[0300] <Solvent> The resin composition in the present invention preferably contains a solvent. Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0301] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0302] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0303] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0304] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0305] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0306] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0307] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0308] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0309] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0310] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0311] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition in the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method.

[0312] The resin composition in the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total concentration is within the above range.

[0313] <Metal Adhesion Improver> The resin composition in the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0314] [Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062-0073 of Japanese Patent Publication No. 2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060-0061 of Japanese Patent Publication No. 2014-191252, the compounds described in paragraphs 0045-0052 of Japanese Patent Publication No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and the compounds described in paragraphs 0067-0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. It is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0315] [ka]

[0316] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

[0317] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0318] Furthermore, other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0319] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content is within the above range.

[0320] <Migration inhibitor> The resin composition in the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the film.

[0321] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0322] Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

[0323] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0324] Specific examples of migration inhibitors include the following compounds.

[0325] [ka]

[0326] If the resin composition in the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the resin composition in the present invention.

[0327] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0328] <Polymerization inhibitor> The resin composition in the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0329] Specific polymerization inhibitor compounds include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine monocerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso -1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and compounds described in paragraphs 0031-0046 of International Publication No. 2015 / 125469 may also be used, and this is incorporated herein by reference.

[0330] If the resin composition in the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition in the present invention.

[0331] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0332] <Other additives> The resin composition in the present invention may contain various additives as needed, to the extent that the effects of the present invention are obtained, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregating agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, it is preferable that their total amount be 3% by mass or less of the solid content of the resin composition in the present invention.

[0333] [Surfactants] Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0334] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the efficiency of the liquid can be further improved. Specifically, when forming a film using a coating solution to which a surfactant-containing composition has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0335] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (all manufactured by DIC Corporation), Florard FC430, FC431, FC171, Novec FC4430, FC4432 (all manufactured by 3M Corporation) Examples include Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Corporation), etc. As fluorine-based surfactants, compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503 may also be used, and the contents of these are incorporated herein. Block polymers can also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Publication No. 2011-89090, the details of which are incorporated herein by reference. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka]

[0336] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorine-based surfactants can also be obtained by using fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0337] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0338] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BIC Chemie Co., Ltd.).

[0339] Examples of hydrocarbon-based surfactants include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T, etc. (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0340] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0341] Examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymers Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0342] Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0343] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0344] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after coating.

[0345] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0346] When the resin composition in the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition in the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[0347] [Thermal polymerization initiator] The resin composition in the present invention may contain a thermal polymerization initiator, and in particular may contain 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. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance. In addition, the photopolymerization initiators mentioned above may also have the function of initiating polymerization by heat and may be added as thermal polymerization initiators.

[0348] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the contents of which are incorporated herein by reference.

[0349] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition in the present invention. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0350] [Inorganic particles] The resin composition in the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0351] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter for inorganic particles is both the primary particle diameter and the volume-average particle diameter. The volume-average particle diameter can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement methods are difficult, measurements can also be performed using centrifugal sedimentation, X-ray transmission, or laser diffraction / scattering methods.

[0352] [UV absorber] The resin composition in the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate, while examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0353] Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2-hydroxy(hydroxy) Examples include bis(hydroxyphenyl)triazine compounds such as c-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0354] In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types. The resin composition in the present invention may or may not contain an ultraviolet absorber. If it does contain an ultraviolet absorber, the amount of ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the resin composition in the present invention.

[0355] [Organotitanium compounds] The resin composition of this embodiment may contain an organotitanium compound. By including an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0356] Examples of usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate). II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0357] In particular, from the viewpoint of achieving better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0358] When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0359] [Antioxidant] The resin composition in the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. Preferred substituents are substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Furthermore, compounds having both a phenol group and a phosphite ester group within the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 may also be used as antioxidants, and this information is incorporated herein by reference. Additionally, the resin composition in this invention may optionally contain a latent antioxidant. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100 to 250°C or at 80 to 200°C in the presence of an acid / base catalyst, thereby removing the protecting group.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219, the contents of which are incorporated herein by reference. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by formula (3).

[0360] [ka]

[0361] In general formula (3), R 5 R represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 k represents a 1-4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2-10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0362] The compound represented by formula (3) suppresses the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins. Furthermore, it can suppress metal oxidation by providing rust prevention to metal materials.

[0363] Since it can act on both resin and metal materials simultaneously, k is more preferably an integer between 2 and 4. 7Examples of these groups include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may also have substituents. Among these, alkyl ether groups and -NH- groups are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- groups are more preferred from the viewpoint of interaction with the resin and metal adhesion due to metal complex formation.

[0364] Examples of compounds represented by general formula (3) include the following, but are not limited to the structures shown below.

[0365] [ka]

[0366] [ka]

[0367] [ka]

[0368] [ka]

[0369] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to the resin. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

[0370] [Anti-coagulation agent] The resin composition of this embodiment may optionally contain an anti-flocculation agent. Examples of anti-flocculation agents include sodium polyacrylate.

[0371] In the present invention, one type of anticoagulant may be used alone, or two or more types may be used in combination. The resin composition in the present invention may or may not contain an anti-flocculation agent. If it does contain an anti-flocculation agent, the amount of the anti-flocculation agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, relative to the total solid content mass of the resin composition in the present invention.

[0372] [Phenol compounds] The resin composition of this embodiment may optionally contain phenolic compounds. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0373] In this invention, a single phenolic compound may be used alone, or two or more compounds may be used in combination. The resin composition in the present invention may or may not contain a phenolic compound. If it does contain a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the resin composition in the present invention.

[0374] [Other polymer compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0375] In this invention, the other polymer compounds may be used individually or in combination of two or more. The resin composition in the present invention may or may not contain other polymer compounds. If other polymer compounds are included, the content of these other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content mass of the resin composition in the present invention.

[0376] <Properties of resin compositions> The viscosity of the resin composition in this invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm 2 / s~12,000mm 2 / s is preferred, and 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500mm 2 / s~8,000mm 2 / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm 2 If the rate is 1 / s or higher, it is easy to coat the film thickness required for, for example, as an insulating film for rewiring, and 12,000 mm 2 If the rate is less than or equal to / s, an excellent coating film can be obtained on the coated surface.

[0377] <Restrictions on substances contained in resin compositions> The water content of the resin composition in the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the storage container.

[0378] From the viewpoint of insulating properties, the metal content of the resin composition in the present invention is preferably less than 5 ppm (parts per million) by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0379] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0380] In the present invention, considering its application as a semiconductor material, the content of halogen atoms in the resin composition is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. Methods for adjusting the halogen atom content include ion exchange treatment.

[0381] Furthermore, from the viewpoint of adhesion of the cured product to metal, it is preferable that the content of components in the resin composition that have a molecular weight of 1000 or less and are different from the solvent is 40% by mass or less relative to the total solid content of the resin composition. The molecular weight is preferably 800 or less, and more preferably 600 or less. The lower limit of the molecular weight is not particularly limited, but can be, for example, 50 or more. Furthermore, the above content is preferably 30% by mass or less, and more preferably 10% by mass or less. The lower limit of the above content is not particularly limited and can be 0% by mass.

[0382] Conventional containers can be used as containers for the resin composition in the present invention. Furthermore, to suppress the incorporation of impurities into the raw materials and the resin composition in the present invention, it is also preferable to use multilayer bottles with an inner wall made of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0383] (Resin composition) The resin composition of the present invention is a resin composition containing a precursor of a cyclized resin, wherein at least one of three films of different thicknesses, when measured by thermomass analysis under the following measurement condition 1, has a mass loss rate of 15% by mass or less. Measurement condition 1: The above resin composition is applied to a silicon substrate to a thickness of 5 μm, 10 μm, or 20 μm, respectively. After drying at 100°C for 5 minutes, a cured product is obtained by heating at 180°C for 2 hours. The temperature is then increased from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and the mass loss rate of the cured product is measured when the temperature is increased from 260°C to 300°C at a rate of 10°C / min. The above mass reduction rate is calculated by the following formula A. Formula A: Mass loss rate (%) = {1 - (mass of the film after heating at 300°C) / (mass of the film at 25°C)} × 100

[0384] According to the resin composition of the present invention, a cured product with excellent adhesion to metal can be obtained. The mechanism by which the above effects are achieved is unknown, but it is speculated to be as follows. The resin composition of the present invention exhibits a mass loss rate of 15% by mass or less for at least one of three films of different thicknesses when measured by thermomass measurement under the above-described measurement conditions 1. Here, if the above mass reduction rate is 15% by mass or less, it is presumed that outgassing is suppressed, and therefore excellent adhesion between the cured material and the metal is considered to be achieved.

[0385] The heating, temperature increase, and maintenance for 2 hours under the above measurement conditions 1 are performed under a nitrogen atmosphere. The above mass loss rate is measured by the method described in the examples.

[0386] Furthermore, the cyclization rate of the cured product obtained under the above measurement condition 1 (the cured product before heating from 25°C to 300°C at a rate of 10°C / min) is preferably 95% or higher, more preferably 98% or higher, and even more preferably 99% or higher. The upper limit of the above cyclization rate is not particularly limited and may be 100%. The cyclization rate is measured by the method described above. If the cyclization rate is within the above range, the migration of metal ions from the metal layer to the cured product, using the uncyclized portion as a penetration path, is suppressed, and it is believed that a cured product with even better adhesion to the metal can be obtained.

[0387] The details of the components contained in the resin composition of the present invention, the properties of the resin composition, etc. are the same as those of the resin composition used in the method for producing the cured product of the present invention described above, and the preferred embodiments are also the same.

[0388] (cured product) The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The details of the cured product of the present invention are the same as the details of the cured product obtained in the method for producing the cured product of the present invention described above, and the preferred embodiments are also the same.

[0389] (Laminate and method for manufacturing the laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate of the present invention is a laminate comprising two or more layers made of a cured material, and may be a laminate comprising three or more layers. Of the two or more layers of the cured material contained in the laminate, at least one is made of the cured material of the present invention. From the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to such shrinkage, it is also preferable that all layers of the cured material contained in the laminate are made of the cured material of the present invention.

[0390] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the laminate of the present invention multiple times.

[0391] The laminate of the present invention comprises two or more layers made of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin, and at least one of the layers made of the cured product is made of the cured product of the present invention. In this case, a preferred embodiment of the present invention is one in which all layers made of the cured material contained in the laminate are layers made of the cured material of the present invention. The laminate of the present invention preferably comprises two or more layers made of a cured material, with a metal layer included between any of the layers made of the cured material. The metal layer is preferably formed by the metal layer formation process described above. In other words, the method for manufacturing a laminate of the present invention preferably further includes a metal layer formation step in which a metal layer is formed on a layer made of a cured product during multiple processes for manufacturing a cured product. Preferred embodiments of the metal layer formation step are as described above. As an example of the above-mentioned laminate, a preferred laminate is one that includes at least three layers in which a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order. Preferably, both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may be compositions with the same composition or compositions with different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

[0392] <Lamination process> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of the pattern (resin layer) or metal layer: (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. However, the film formation step in (a) and at least one of the heating step and post-development exposure step in (d) may be repeated. Furthermore, a metal layer formation step (e) may be included after at least one of the heating step and post-development exposure step. Needless to say, the lamination process may also include the above-mentioned drying step, etc., as appropriate.

[0393] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0394] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may or may not have the same composition, shape, film thickness, etc.

[0395] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and at least one of the post-development exposure steps, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and at least one of the post-development exposure steps, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0396] (Surface activation treatment process) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer. The surface activation treatment step is usually performed after the metal layer formation step, but the surface activation treatment step may be performed on the resin composition layer after the development step (preferably after at least one of the heating step and the post-development exposure step) before the metal layer formation step is performed. The surface activation treatment may be performed on at least a portion of the metal layer, on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on that surface can be improved. Furthermore, it is preferable to perform the surface activation treatment on part or all of the resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion between the surface-activated surface and the metal layer or resin layer can be improved. In particular, when the resin composition layer has hardened, such as when negative type development is performed, it is less susceptible to damage from the surface treatment and adhesion is easily improved. Surface activation treatments can be specifically selected from plasma treatment with various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, etching treatment with CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, ultraviolet (UV) ozone method, immersion in an aqueous hydrochloric acid solution to remove the oxide film followed by immersion in an organic surface treatment agent containing at least one amino group and one thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is 500 to 200,000 J / m 2 Preferably, 1,000 to 100,000 J / m 2 More preferably, 10,000 to 50,000 J / m 2 Most preferable.

[0397] (Semiconductor devices and methods for manufacturing the same) Furthermore, the present invention also discloses semiconductor devices comprising a cured product of the present invention or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a cured product of the present invention, or a method for manufacturing a semiconductor device that includes a method for manufacturing a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference. [Examples]

[0398] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0399] (Example of combination) <Synthesis of polyimide precursor resin (SA-1)> 19.1 g (61.2 mmol) of 4,4'-oxydiphthalic acid dianhydride, 12.3 g (94 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 21.5 g (272 mmol) of pyridine, and 80 g of diglyceride were mixed and stirred at 25°C. Subsequently, 2.18 g (30.6 mmol) of pyrrolidine dissolved in 10 g of diglyceride was added dropwise over 30 minutes, and the mixture was stirred at 60°C for 4 hours, then cooled to 25°C. After the reaction solution was cooled to -10°C, 15.3 g (127 mmol) of thionyl chloride was added dropwise over 90 minutes, and the mixture was stirred for 2 hours. Next, 18.8 g (51 mmol) of 4,4'-bis(4-aminophenoxy)biphenyl was dissolved in 100 mL of NMP and added dropwise over 1 hour, followed by stirring for 2 hours. Then, 9.0 g (195 mmol) of ethanol was added, the mixture was stirred for 2 hours, 50 mL of tetrahydrofuran was added, and the polyimide precursor resin was precipitated in 3 liters of water. The water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was filtered and obtained, then stirred again in 4 liters of water for 30 minutes, filtered again, and the obtained polyimide precursor resin was dried under reduced pressure at 45°C for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300 mL of tetrahydrofuran, 50 g of ion exchange resin was added, and the mixture was stirred for 6 hours. Then, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was filtered and dried at 45°C for 2 days to obtain polyimide precursor (SA-1). The weight-average molecular weight of the obtained polyimide precursor SA-1 was 23,100, and the number-average molecular weight was 8,900. The structure of SA-1 is presumed to be represented by the following formula (SA-1). [ka]

[0400] <Synthesis of polyimide precursor resins (SA-2 to SA-4)> SA-2 to SA-4 were synthesized in the same manner as SA-1, except that the types and molar ratios of the amine (pyrrolidine in the synthesis of SA-1) and alcohol (2-hydroxyethyl methacrylate in the synthesis of SA-1) were changed as shown in the table below, and the carboxylic acid anhydride (4,4'-oxydiphthalic acid dianhydride in the synthesis of SA-1) and diamine (4,4'-bis(4-aminophenoxy)biphenyl in the synthesis of SA-1) were appropriately changed. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of these resins are listed in the Mw and Mn columns of the table below, respectively. The structures of SA-2 to SA-4 are presumed to be represented by the following equations (SA-2) to (SA-4), respectively. In the following equations, the subscripts in parentheses representing the repeating units represent the molar ratio of each repeating unit.

[0401] [Table 1] [ka]

[0402] <Synthesis of polyamide-imide precursor resin (SA-5)> 14.8 g (47.6 mmol) of 4,4'-oxydiphthalic acid dianhydride, 10.68 g (81.9 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 16.7 g (210 mmol) of pyridine, and 60 g of diglyceride were mixed and stirred at 25°C. Subsequently, 1.02 g (14.3 mmol) of pyrrolidine dissolved in 10 g of diglyceride was added dropwise over 30 minutes, and the mixture was stirred at 60°C for 4 hours, then cooled to 25°C. After the reaction solution was cooled to -10°C, 11.9 g (99 mmol) of thionyl chloride was added dropwise over 90 minu...

Claims

1. A film-forming step involves applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and A method for producing a cured product, comprising a heating step of heating the aforementioned film at a heating temperature of 180°C or lower, The mass loss rate expressed by the following formula A when the film after the heating step is heated from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then heated from 260°C to 300°C at a rate of 10°C / min is 15% or less. The cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the resulting cured product is 95% or more. The precursor of the cyclized resin comprises a resin having at least one of the repeating units represented by the following formula (1-1) and the repeating units represented by the following formula (1-2). A method for manufacturing a cured product. Formula A: Mass loss rate (%) = {1 - (mass of the film after heating at 300°C) / (mass of the film at 25°C)} × 100 【Chemistry 1】 In formula (1-1) or formula (1-2), W １ represents a divalent organic group, X １ represents a tetravalent organic group, and R １ to R ３ each independently represent a group represented by the following formula (3-1) or a group represented by formula (3-2), and W ２ represents a divalent organic group, X ２ represents a trivalent organic group, and the resin comprises at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-1) in which at least one of R １ and R ２ is a group represented by formula (3-1), and a repeating unit represented by formula (1-2) in which R ３ is a group represented by formula (3-1). 【Chemistry 2】 In formula (3-1) and formula (3-2), Z １ and Z ２ Each of these independently represents an organic group, Z １ and Z ２ They may bond to form a ring structure, A ２ represents an oxygen atom or -NH-, R １１３ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures.

2. A film-forming step involves applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and A method for producing a cured product, comprising a heating step of heating the aforementioned film at a heating temperature of 180°C or lower, The process further includes an exposure step for selectively exposing the film between the film formation step and the heating step, The process further includes a developing step between the exposure step and the heating step, in which the exposed film is developed with a developing solution to form a pattern. The developer comprises an organic solvent and a base, The mass loss rate expressed by the following formula A when the film after the heating step is heated from 25°C to 260°C at a rate of 10°C / min, maintained at 260°C for 15 minutes, and then heated from 260°C to 300°C at a rate of 10°C / min is 15% or less. The cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the resulting cured product is 95% or more. The precursor of the cyclized resin is at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. The polyimide precursor comprises a repeating unit represented by formula (2), The polybenzoxazole precursor comprises a repeating unit represented by formula (3), The polyamide-imide precursor comprises a repeating unit represented by formula (PAI-2), The aforementioned organic solvent is a ketone, The content of the organic solvent relative to the total mass of the developer is 70% by mass or more. A method for manufacturing a cured product. Formula A: Mass loss rate (%) = {1 - (mass of the film after heating at 300°C) / (mass of the film at 25°C)} × 100 【Transformation 3】 In formula (2), A1 and A2 each independently represent an oxygen atom or -NRz-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, R113 and R114 each independently represent a hydrogen atom or a monovalent organic group, and Rz represents a hydrogen atom or a monovalent organic group. 【Chemistry 4】 In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. 【Transformation 5】 In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NR z-, R 113 represents a hydrogen atom or a monovalent organic group, and R z represents a hydrogen atom or a monovalent organic group.

3. A method for producing a cured product according to claim 1 or 2, wherein the heating temperature in the heating step exceeds 150°C.

4. A method for producing a cured product according to claim 1 or 2, wherein the mass reduction rate is 10% or less.

5. A method for producing a cured product according to claim 1 or 2, wherein the mass reduction rate is 5% or less.

6. A method for producing a cured product according to claim 1 or 2, wherein the cyclization rate is 98% or more.

7. The method for producing a cured product according to claim 1 or 2, wherein the film after the heating step is a polyimide film.

8. The method for producing a cured product according to claim 1, further comprising an exposure step of selectively exposing the film between the film formation step and the heating step.

9. The method for producing a cured product according to claim 8, further comprising a developing step between the exposure step and the heating step, in which the exposed film is developed with a developing solution to form a pattern.

10. The method for producing a cured product according to claim 9, wherein the developing solution contains an organic solvent.

11. The method for producing a cured product according to claim 9, wherein the developing step is a step of forming a negative-type pattern.

12. The method for producing a cured product according to claim 9, wherein the developing solution contains a base.

13. A method for producing a cured product according to claim 9, comprising a processing step of bringing a processing solution containing a base into contact with the pattern between the developing step and the heating step.

14. The method for producing a cured product according to claim 1 or 2, wherein the resin composition contains a photosensitive agent.

15. The method for producing a cured product according to claim 1 or 2, wherein the resin composition contains a solvent, and the content of the precursor of the cyclized resin is 70% by mass or more with respect to the total solid content of the resin composition.

16. The method for producing a cured product according to claim 1 or 2, wherein the resin composition contains a polymerizable compound having a boiling point of 270°C or higher at 1 atmosphere.

17. The method for producing a cured product according to claim 16, wherein the polymerizable compound having a boiling point of 270°C or higher at 1 atmosphere is a compound having three or more (meth)acrylate groups.

18. A method for producing a cured product according to claim 1 or 2, wherein the content of a component having a molecular weight of 1000 or less, which is different from the solvent, is 30% by mass or less with respect to the total solid content of the resin composition.

19. The precursor of the cyclized resin comprises a resin having at least one of the repeating units represented by the following formula (1-1) and the repeating units represented by the following formula (1-2). A method for producing a cured product according to claim 2. 【Transformation 6】 In formula (1-1) or formula (1-2), W １ This represents a divalent organic group, X １ represents a tetravalent organic group, R １ ~R ３ Each of these independently represents a group represented by formula (3-1) or a group represented by formula (3-2) below, W ２ represents a divalent organic group, X ２ R represents a trivalent organic group, and the resin is a repeating unit represented by formula (1-1). １ and R ２ A repeating unit in which at least one of is a base represented by formula (3-1), and a repeating unit represented by formula (1-2) R ３ It includes at least one repeating unit selected from the group of repeating units whose base is represented by equation (3-1). 【Transformation 7】 In formula (3-1) and formula (3-2), Z １ and Z ２ Each of these independently represents an organic group, Z １ and Z ２ They may bond to form a ring structure, A ２ represents an oxygen atom or -NH-, R １１３ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures.

20. A method for manufacturing a laminate, comprising repeating the method for manufacturing a cured product described in claim 1 or 2 a plurality of times.

21. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 1 or 2.

22. A resin composition containing a precursor of a cyclized resin, The precursor of the cyclized resin comprises a resin having at least one of the repeating units represented by the following formula (1-1) and the repeating units represented by the following formula (1-2). When thermal mass measurement is performed under the measurement conditions 1 below, at least one of the three films with different thicknesses has a mass loss rate of 15% by mass or less. resin composition; Measurement condition 1: The resin composition is applied to a silicon substrate to a thickness of 5 μm, 10 μm, or 20 μm, respectively. After drying at 100°C for 5 minutes, a cured product is obtained by heating at 180°C for 2 hours. The cured product is then returned to 25°C, and its temperature is increased from 25°C to 260°C at a rate of 10°C / min. The temperature is maintained at 260°C for 15 minutes, and the mass loss rate of the cured product is measured when the temperature is increased from 260°C to 300°C at a rate of 10°C / min. The aforementioned mass reduction rate is calculated by the following formula A. Formula A: Mass loss rate (%) = {1 - (mass of the film after heating at 300°C) / (mass of the film at 25°C)} × 100 【Transformation 8】 In formula (1-1) or formula (1-2), W １ This represents a divalent organic group, X １ represents a tetravalent organic group, R １ ~R ３ Each of these independently represents a group represented by formula (3-1) or a group represented by formula (3-2) below, W ２ represents a divalent organic group, X ２ R represents a trivalent organic group, and the resin is a repeating unit represented by formula (1-1). １ and R ２ A repeating unit in which at least one of is a base represented by formula (3-1), and a repeating unit represented by formula (1-2) R ３ It includes at least one repeating unit selected from the group of repeating units whose base is represented by equation (3-1). 【Chemistry 9】 In formula (3-1) and formula (3-2), Z １ and Z ２ Each of these independently represents an organic group, Z １ and Z ２ They may bond to form a ring structure, A ２ represents an oxygen atom or -NH-, R １１３ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures.

23. A cured product obtained by curing the resin composition according to claim 22.

24. It comprises two or more layers made of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin, At least one of the layers made of the cured material is a layer made of the cured material described in claim 23. Laminated structure.

25. A cured product according to claim 23 or a laminate according to claim 24, Semiconductor devices.

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