Methods for manufacturing hardened materials, methods for manufacturing multilayers, and methods for manufacturing semiconductor devices.

Abstract

This invention provides a method for manufacturing a cured material that exhibits excellent elongation at break even when cured at low temperatures, a method for manufacturing a laminate comprising the above-described method for manufacturing a cured material, and a method for manufacturing a semiconductor device comprising the above-described method for manufacturing a cured material or the above-described method for manufacturing a laminate. The methods for manufacturing a cured material, a laminate comprising the above-described method for manufacturing a cured material, and a semiconductor device comprising the above-described method for manufacturing a cured material or the above-described method for manufacturing a laminate include: a film formation step, wherein a specific photosensitive resin composition is applied to a substrate to form a film; an exposure step; a development step; a processing step, wherein an alkaline processing solution containing at least one compound selected from the group consisting of alkali and alkali-generating agents is brought into contact with the pattern; and a heating step, wherein the water content in the alkaline processing solution is 50% by mass or less.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a cured material, a photosensitive resin composition, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device. Prior Technology

[0002] Resins such as polyimide possess excellent heat resistance and insulation properties, making them suitable for a wide range of applications. While there are no particular limitations on these applications, examples include the use of patterns containing these resins as insulating films, sealing materials, or protective films in the context of actual semiconductor device mounting. Furthermore, patterns containing these resins can also be used as base films or cover films for flexible substrates.

[0003] For example, in the above-described applications, resins such as polyimide are used in the form of photosensitive resin compositions containing polyimide precursors. The photosensitive resin composition is applied to a substrate by means of coating, and then exposed, developed, heated, etc., as needed, thereby forming a hardened polyimide precursor that is amide-modified on the substrate. Photosensitive resin compositions can be applied using known coating methods, and can be developed to form fine patterns and complex shapes. Therefore, the design freedom of cured products is high, and their manufacturing adaptability is excellent. Considering this excellent manufacturing adaptability in addition to the high performance of polyimide, there is growing anticipation for the industrial application development of manufacturing methods for cured products using photosensitive resin compositions containing polyimide precursors.

[0004] For example, Patent Document 1 describes a pattern forming method characterized by exposing a photosensitive polyimide layer on a substrate to photocuring it into a suitable pattern, followed by developing it to remove unexposed portions, immersing the substrate with the photocured polyimide pattern layer in a rinsing solution containing at least 5-30% by volume of a primary aliphatic amine compound and 2-20% by volume of an aprotic alkaline solvent to rinse the substrate, and finally heat-treating the substrate with the photocured polyimide layer removed from the rinsing solution at high temperature.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 1-221741

[0006] Previously, a process was carried out by applying a photosensitive resin composition containing a polyimide precursor onto a substrate to form a film, exposing and developing the film, and then heating to amide the precursor to produce a cured film. This amide oxidation improves the mechanical properties of the film (e.g., elongation at break) and enhances reliability in modules. In the manufacture of the aforementioned hardened material, it is desirable to provide a method for manufacturing a hardened material that can achieve excellent elongation at break even when hardening is performed at low temperatures. Specifically, for example, the aforementioned hardened material can be used as an interlayer insulating film for the rewiring layer. Among these advancements, the substrate using the aforementioned insulating film has expanded from an 8-inch wafer size to a 12-inch panel size. Furthermore, in order to install wiring such as copper wiring, the number of layers to be stacked has gradually increased from 1 layer to 2, 3, 4, and 5 layers. With the increasing size of the substrate and the increase in the number of polyimide layers during this manufacturing process, the warping of the wafer or panel becomes significant, making it desirable to perform the aforementioned heating at low temperatures (e.g., below 230°C). However, when the above heating is performed at low temperatures, the amide oxidation cannot be fully carried out, and the elongation at break of the film sometimes decreases.

[0007] To date, attempts have been made to introduce alkali into photosensitive resin compositions in order to ensure sufficient amide imidization even when heated at low temperatures. When an alkali is added directly to a photosensitive resin composition, the polyimide precursor will undergo amide imidization even when the photosensitive resin composition is stored, and sometimes the viscosity of the composition changes significantly. When a photoalkali generator, which is a precursor to an alkali, is added, during exposure, acids and free radicals that promote negative image formation, as well as alkalis that act as inhibitors of acids and free radicals, are simultaneously generated in the exposure section, sometimes accompanied by a decrease in sensitivity. Furthermore, from a formulation perspective, it is difficult to add large amounts of alkali generators to the composition, and the effect of promoting acetylation upon heating is limited. Summary of the Invention

[0008] The purpose of this invention is to provide a method for manufacturing a hardened material that can achieve excellent elongation at break even when hardened at low temperatures, a method for manufacturing a multilayer comprising the above-described method for manufacturing a hardened material, and a method for manufacturing a semiconductor device comprising the above-described method for manufacturing a hardened material or the above-described method for manufacturing a multilayer.

[0009] Examples of representative embodiments of the present invention are shown below. <1> A method for manufacturing a hardened material, comprising: The film forming step involves applying a photosensitive resin composition comprising a polyimide precursor having repeating units represented by the following formula (2) and a photopolymerization initiator onto a substrate to form a film; The exposure step involves selectively exposing the aforementioned film. The developing step involves developing the exposed film with a developing solution to form a pattern; The processing step involves contacting the pattern with an alkaline treatment solution containing at least one compound selected from the group consisting of alkalis and alkali-generating agents; and The heating step involves heating the pattern obtained after the above processing steps. The water content is less than 50% by mass relative to the total mass of the above-mentioned alkaline treatment solution. [Chemical Formula 1] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R113 and R114 independently represent monovalent organic groups, R115 represents tetravalent organic groups, and R111 represents divalent organic groups. <2> like <1> The method for manufacturing the hardened material, wherein the alkaline treatment solution is a rinsing solution, and the treatment step is a rinsing step of cleaning the pattern with the rinsing solution. <3> like <1> or <2> The method for manufacturing the hardened material, wherein the alkaline treatment solution contains an organic base as the base. <4> like <1> to <3> The method for manufacturing the hardened material according to any one of the claims, wherein the alkaline treatment solution contains a secondary or tertiary amine as the alkali. <5> like <1> to <4> The method for manufacturing the hardened material according to any one of the claims, wherein the heating step is a step of promoting the amide formation of the polyamide precursor within the pattern by heating using the action of at least one compound selected from the group including the alkali and alkali generated from the alkali generating agent. <6> like <1> to <5> The method for manufacturing the hardened material according to any one of the above-mentioned heating steps, wherein the heating temperature in the heating step is 120~230°C. <7> like <1> to <6> The method for manufacturing a hardened material according to any one of the claims, wherein the developing step is a step of supplying or continuously supplying the developing solution to the exposed film by spraying. <8> like <1> to <7> The method for manufacturing a hardened material according to any one of the claims, wherein the above-mentioned processing step is a step of supplying or continuously supplying the above-mentioned alkaline treatment solution to the above-mentioned developed pattern by spraying. <9> like <1> to <8> The method for manufacturing a hardened material according to any one of the above-described methods, wherein the development in the development step is negative development. <10> A method for manufacturing a laminate, which involves repeating the process multiple times. <1> to <9> The method for manufacturing the hardened material as described in any one of the claims. <11> like <10> The method for manufacturing the laminate further includes a metal layer forming step, which forms a metal layer on the hardened material during the aforementioned multiple processes of manufacturing the hardened material. <12> A method for manufacturing a semiconductor device, comprising: <1> to <9> The method for manufacturing the hardened material as described in any one of the above methods or <10> or <11> The method for manufacturing the laminated body. [Invention Effects]

[0010] According to the present invention, a method for manufacturing a hardened material that can obtain excellent elongation at break even when hardened at low temperature is provided; a method for manufacturing a multilayer comprising the above-described method for manufacturing a hardened material; and a method for manufacturing a semiconductor device comprising the above-described method for manufacturing a hardened material or the above-described method for manufacturing a multilayer. Implementation

[0011] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” represents the range within which the values ​​recorded before and after “~” are respectively taken as the lower limit and upper limit. In this specification, the term "step" not only refers to an independent step, but also includes steps that cannot be clearly distinguished from other steps, as long as the intended function of the step can be achieved. Regarding the designation of groups (atomic groups) in this specification, the designations for unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise stated, “exposure” includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation. In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acrylyl” means “acrylyl” and “methacrylyl” or either one. In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, total solids content refers to the total mass of all components of the composition, excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of all components other than the solvent relative to the total mass of the composition. In this instruction manual, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined using gel osmosis chromatography (GPC) and are defined as polystyrene equivalents. In this instruction manual, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise stated, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. In cases where THF is unsuitable as an eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise stated, the detection in GPC assays uses a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when referring to the positional relationship of the layers constituting the laminate as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the plurality of layers in question. That is, a third layer or third element may be sandwiched between the reference layer and the other layers mentioned above, and the reference layer does not need to be in contact with the other layers. Furthermore, unless otherwise stated, the direction in which the layers are gradually stacked on the substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, this up-down orientation is for the convenience of explaining this instruction manual. In actual practice, the "up" orientation in this instruction manual may also be different from "vertically up". In this specification, unless otherwise stated, each component included in the composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to that component. In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of the better state sample is referred to as the superior state sample.

[0012] (Method for manufacturing hardened material) The method for manufacturing the cured material of the present invention includes: a film forming step, wherein a photosensitive resin composition comprising a polyimide precursor (hereinafter also referred to as "specific resin") having repeating units represented by the following formula (2) and a photopolymerization initiator is applied to a substrate to form a film; an exposure step, wherein the film is selectively exposed; a development step, wherein the exposed film is developed by a developing solution to form a pattern; a treatment step, wherein an alkaline treatment solution comprising at least one compound selected from the group including alkali and alkali generating agents is brought into contact with the pattern; and a heating step, wherein the pattern after the treatment step is heated, wherein the water content is 50% by mass or less relative to the total mass of the alkaline treatment solution.

[0013] According to the method for manufacturing the hardened material of the present invention, a hardened material with excellent elongation at break can be obtained even when hardening is carried out at low temperature. The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0014] In the method for manufacturing the hardened material of the present invention, a processing step is included, wherein an alkaline treatment liquid containing at least one compound selected from the group consisting of alkalis and alkali generating agents is brought into contact with the pattern. It is believed that by using such an alkaline treatment solution, during the processing steps (e.g., rinsing), at least one of the alkali and alkali generating agent contained in the alkaline treatment solution penetrates into the pattern obtained by development. It is speculated that the polyimide precursor is easily amided even at low temperatures by the action of at least one of the alkali or alkali generating agent transferred from the above-mentioned alkaline treatment solution to the pattern, and can achieve a significant reduction in low temperature when heated.

[0015] Patent Document 1 does not describe the following: using a photosensitive resin composition comprising a polyimide precursor having repeating units represented by the above formula (2) and a photopolymerization initiator, and processing the developed film with an alkali-containing treatment solution comprising at least one compound selected from the group including alkali and alkali generating agents to form a pattern. The method for manufacturing the hardened material of the present invention will be described in detail below.

[0016] <Membrane Formation Steps> The method for manufacturing the cured material of the present invention includes a film forming step of applying a photosensitive resin composition onto a substrate to form a film. The details of the photosensitive resin composition used in this invention will be described later.

[0017] [Substrate] The type of substrate can be appropriately selected according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, 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, any of the substrates formed of metal and substrates with metal layers formed by electroplating or vapor deposition); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred. Furthermore, layers such as a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) may be provided on the surface of such substrates. Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular. For the dimensions of the substrate, if it is circular, the diameter is, for example, 100~450mm, preferably 200~450mm. If it is rectangular, the length of the shorter side is, for example, 100~1000mm, preferably 200~700mm. Furthermore, as a substrate, a plate-shaped substrate (substrate) can be used, preferably a panel-shaped substrate.

[0018] Furthermore, in cases where a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer formed from a hardened material) or a metal layer, the resin layer or the metal layer becomes the substrate.

[0019] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[0020] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating are preferred. From the viewpoints of film thickness uniformity and productivity, spin coating and slot coating are better. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred. For rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for about 10 seconds to 3 minutes. Furthermore, it can also be applied to the method of transferring a coating formed by pre-applying it to a dummy support using the above-mentioned application method onto a substrate. Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferred in this invention. Furthermore, a step can be performed to remove excess film from the ends of the substrate. Examples of such a step include edge bead rinsing (EBR) and back rinse. Alternatively, a pre-wetting step can be used, in which various solvents are applied to the substrate to improve its wettability before the resin composition is applied to the substrate.

[0021] <Drying Steps> After the film formation step (layer formation step), the above-mentioned film can be used in the drying step (drying step) to remove the solvent. That is, the method for manufacturing the hardened material of the present invention may include a drying step, which dries the film formed by the film forming step. Furthermore, it is preferable that the drying step is performed after the film formation step and before the exposure step. The preferred drying temperature for the membrane during the drying process is 50~150℃, more preferably 70℃~130℃, and even more preferably 90℃~110℃. Alternatively, drying can be performed under reduced pressure. For drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 2 minutes to 7 minutes are even better.

[0022] <Exposure Steps> The above-mentioned film is used in the exposure step of selectively exposing the film. That is, the method for manufacturing the cured material of the present invention includes an exposure step, which selectively exposes the film formed by the film forming step. Selective exposure means exposing a portion of the film. Furthermore, through selective exposure, exposed areas (exposed areas) and unexposed areas (unexposed areas) are formed on the film. Regarding the exposure amount, there are no special requirements as long as it can harden the resin composition of the present invention. For example, it is preferred to use an exposure energy of 50 to 10,000 mJ / cm² at a wavelength of 365 nm, and even more preferred to use 200 to 8,000 mJ / cm².

[0023] The exposure wavelength can be appropriately set within the range of 190~1,000nm, with 240~550nm being the optimal range.

[0024] Regarding the exposure wavelength, examples related to the light source include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), and wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet (EUV) lasers (wavelength 13.6nm), (6) electron beams, and (7) YAG lasers with a second harmonic of 532nm and a third harmonic of 355nm. Regarding the resin composition of this invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is even more preferred. This allows for exceptionally high exposure sensitivity. Furthermore, there is no particular limitation on the exposure method, as long as it is an exposure of at least a portion of the film formed by the resin composition of the present invention, but examples include exposure using a photomask and exposure based on direct laser imaging.

[0025] <Post-exposure heating steps> The above-mentioned film can be used in the step of heating after exposure (post-exposure heating step). That is, the method for manufacturing the cured material of the present invention may include a post-exposure heating step, which heats the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50℃~140℃, and even better is 60℃~120℃. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and even better if it is 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, a rate of 1~12℃ / min from the initial heating temperature to the maximum heating temperature is preferred, 2~10℃ / min is even better, and 3~10℃ / min is even more preferred. Furthermore, the heating rate can be adjusted appropriately during the heating process. There are no particular limitations on the heating mechanism used in the post-exposure heating step; commonly known heating plates, ovens, infrared heaters, etc., can be used. Furthermore, it is also better to conduct the process in a low-oxygen environment by allowing inactive gases such as nitrogen, helium, and argon to flow through during heating.

[0026] <Developing Steps> The exposed film is then used in the developing step to form a pattern by developing it with a developing solution. That is, the method for manufacturing the hardened material of the present invention includes a developing step, which uses a developing solution to develop the film exposed by the exposure step to form a pattern. The exposed and unexposed portions of the film are removed by developing the film, thus forming a pattern. The development process that removes the non-exposed portions of the film through the development step is called negative development, while the development process that removes the exposed portions of the film through the development step is called positive development. In this invention, it is preferable that the development step is negative development.

[0027] [Developing solution] Examples of developing solutions used in the developing step include alkaline aqueous solutions or developing solutions containing organic solvents.

[0028] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, 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 (Tetrapropylammonium Hydroxide), tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, with TMAH being more preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0029] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3- Methyl alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate) Esters, such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, such as 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, propylene glycol monopropyl ether acetate, etc., and as ethers, etc. Ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., are preferred examples; as cyclic hydrocarbons, such as aromatic hydrocarbons like toluene, xylene, and anisole, and cyclic terpenes like limonene are preferred examples; as sulfoxides, such as dimethyl sulfoxide is preferred examples; as alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferred examples; and as amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylmethamide are preferred examples. Furthermore, the developing solution contains the base described later, and when the base (e.g., an organic base) is liquid in the environment where the developing solution is used, the base can be used as a solvent and a base.

[0030] When the developer contains an organic solvent, one or more organic solvents may be used. In this invention, it is particularly preferred that the developer contains at least one solvent selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developer contains at least one solvent selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and the developer containing cyclopentanone is the most preferred.

[0031] When the developer contains organic solvents, it is preferable that the organic solvent content is 50% by mass or more relative to the total mass of the developer, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can be 100% by mass.

[0032] -Alkali, alkali generating agent- The developer may contain at least one compound selected from the group consisting of alkalis and alkali-generating agents. Examples of preferred compounds as alkalis and alkali-generating agents include the alkalis and alkali-generating agents contained in the alkali-containing treatment solution described later.

[0033] The developer may further contain other ingredients. Other components include, for example, well-known surfactants and well-known defoamers.

[0034] [Method for supplying developer] Regarding the method of supplying the developer, there are no particular limitations as long as the desired pattern can be formed. Methods include immersing the substrate with the film formed in the developer, using a nozzle to supply the developer to the film formed on the substrate for spin-on immersion development, or continuously supplying the developer. There are no particular limitations on the type of nozzle, and examples include straight nozzles, spray nozzles, and mist nozzles. From the perspectives of developer penetration, non-image area removal, and manufacturing efficiency, the method of supplying developer using a straight nozzle or a continuous supply method using a spray nozzle is preferable. From the perspective of developer penetration into the image area, the method of supplying using a spray nozzle is even better. When using a thin film layer, from the perspectives of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to use a straight nozzle to supply the developer or to use a spray nozzle for continuous supply. From the perspective of developer penetration into the image area, using a spray nozzle for supply is even better. When using thick film layers, considering the permeability of the developer, the removal of non-image areas, and manufacturing efficiency, it is better to use a method of supplying the developer with a straight nozzle or a method of continuous supply with a spray nozzle. Considering the permeability of the developer to the image area, it is better to use a swirling immersion development method where the developer supplied by the nozzle is kept still. The above-mentioned development methods (e.g., spin-dip development and spray development, or a combination of spin-dip development and direct development) can be used simultaneously. Based on this simultaneous use, for example, the film expands due to spin-dip development, allowing the processing solution to easily penetrate. Spray development or mist development then improves the removal of non-image areas. Therefore, it has advantages such as easily achieving improved removal of non-image areas while simultaneously increasing elongation at break through the penetration of the processing solution. Alternatively, after continuously supplying developer using a straight nozzle, the substrate can be rotated to remove the developer from the substrate. After rotation drying, the substrate can be continuously supplied again using a straight nozzle, and the substrate can be rotated to remove the developer from the substrate. This process can be repeated several times. Furthermore, as a method for supplying the developer in the developing step, steps such as continuously supplying the developer to the substrate, keeping the developer in a substantially static state on the substrate, vibrating the developer on the substrate using ultrasound or the like, and combinations thereof can be employed. Among these, the developing step is preferably a step in which the developing solution is supplied or continuously supplied to the exposed film by means of diffusion radiation such as spraying or sprinkling.

[0035] The optimal development time is 10 seconds to 10 minutes, with 20 seconds to 5 minutes being even better. There are no specific requirements for the temperature of the developing solution during development, but it is best performed at 10 to 45°C, and even better at 18 to 30°C.

[0036] <Processing Steps> The method for manufacturing the hardened material of the present invention includes a processing step in which an alkaline treatment solution containing at least one compound selected from the group consisting of alkalis and alkali generating agents is brought into contact with the pattern described above. The preferred treatment step is to clean the pattern with the alkaline solution described above. Furthermore, rinsing solutions containing alkali are preferred. Furthermore, the aforementioned alkaline treatment solution is a rinsing solution, and the aforementioned treatment step is preferably a rinsing step of cleaning the pattern with the aforementioned rinsing solution. That is, it is preferable to use a rinsing step to clean the pattern (the pattern obtained by the developing step) with a rinsing solution containing at least one compound selected from the group including alkali and alkali generating agents. Furthermore, the above-mentioned processing steps may be performed, for example, after the "Other Rinsing Steps" described later.

[0037] [Alkali-containing treatment solution] In the method for manufacturing the hardened material of the present invention, the water content in the alkaline treatment solution is 50% by mass or less relative to the total mass of the alkaline treatment solution. The water content is preferably 20% by mass or less, even better 10% by mass or less, further better 5% by mass or less, and particularly good 2% by mass or less. There is no specific limit to the lower limit of the water content mentioned above; it can also be 0 by mass.

[0038] As an alkaline treatment solution, for example, a solvent can be used that is a solvent contained in the developer and a solvent different from the solvent contained in the developer (e.g., an organic solvent different from the organic solvent contained in the developer) and contains at least one compound selected from the group including alkali and alkali generating agents.

[0039] -Alkali- From the viewpoint of reliability when remaining in the hardened film (adhesion to the substrate when the hardened material is further heated), organic bases are preferred as a better alkali. Furthermore, as a base, a base with an amino group is preferred, and amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides are preferred. However, in order to promote the amide imidization reaction, primary amines, secondary amines, and tertiary amines are preferred, with secondary or tertiary amines being even better, and tertiary amines being the best. From the perspective of the mechanical properties (elongation at break) of the hardened material, it is preferable that the alkali does not easily remain in the hardened film (the obtained hardened material). From the perspective of promoting acetylation, it is preferable that the amount of alkali that does not easily decrease due to vaporization before heating is preferable. Therefore, the boiling point of the alkali is preferably 30℃ to 350℃ at normal pressure (101,325 Pa), even better at 80℃ to 270℃, and further better at 100℃ to 230℃. Furthermore, it is preferable that the boiling point of the alkali is higher than the temperature by subtracting 20°C from the boiling point of the organic solvent contained in the alkali-containing treatment solution, and even better that it is higher than the boiling point of the organic solvent contained in the alkali-containing treatment solution. For example, when the boiling point of the organic solvent is 100°C, it is preferable that the boiling point of the alkali used is 80°C or higher, and even better if it is 100°C or higher.

[0040] For the DMSO (dimethyl sulfoxide) of the conjugate acid of the above-mentioned base, a pKa of 1 or higher is preferred, and 3 or higher is even more preferred. There is no particular upper limit to the above-mentioned pKa, but 20 or lower is preferred. When the conjugate acid of the above-mentioned base has a plurality of pKa values ​​in DMSO, it is preferable that at least one of them is within the above-mentioned range. Wherein, pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and can be found in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; eds.: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these publications, the pKa will be calculated using ACD / pKa software (ACD / Labs) and the structural formula.

[0041] Specific examples of alkalis contained in alkaline treatment solutions include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-Methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine.

[0042] When alkali is present, the alkali content relative to the total mass of the alkali-containing 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, when the alkali is not liquid at 10~30℃, an alkali content of 0.3~30% by mass is preferred, and 0.5~20% by mass is even better. One type of alkali may be used alone, or two or more types may be used simultaneously. When two or more types of alkali are used simultaneously in an alkali-containing treatment solution, it is preferable that their total content be within the range described above.

[0043] -Alkali generating agent- Alkaline treatment solutions may contain alkali-generating agents. Examples of alkali generating agents include light-induced alkali generating agents and heat-induced alkali generating agents, with heat-induced alkali generating agents being preferred. As the aforementioned photoalkali generating agent or thermal alkali generating agent, for example, the photoalkali generating agent or thermal alkali generating agent described as a component included in the photosensitive resin composition described later can be used without particular limitation.

[0044] When an alkali-generating agent is included, the content of the alkali-generating agent relative to the total mass of the alkali-containing treatment liquid 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. One type of alkali-generating agent may be used alone, or two or more may be used simultaneously. When two or more alkali-generating agents are used simultaneously in an alkali-containing treatment solution, it is preferable that their total content be within the range described above.

[0045] Examples of organic solvents, and of the form of esters, preferably include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, alkyl 3-alkoxypropionic acid). Ethyl hydroxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate) ethyl 2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, Examples of preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and anisole; cyclic terpenes such as limonene; dimethyl sulfoxide as a sulfide; methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol as alcohols; and N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylmethamide as acetamides. Furthermore, when the aforementioned alkali (e.g., organic alkali) is liquid in the environment of using an alkali-containing treatment solution, the aforementioned alkali can be used as a solvent and alkali.

[0046] When the alkaline treatment solution contains organic solvents, one or more organic solvents may be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are further preferred.

[0047] When the alkaline treatment solution contains organic solvents, it is preferable that 50% or more by mass of the alkaline treatment solution is an organic solvent, more preferably 70% or more by mass, and even more preferably 90% or more by mass. Alternatively, the alkaline treatment solution may contain 100% by mass of organic solvents.

[0048] Alkaline treatment solutions may further contain other components. Other components include, for example, well-known surfactants and well-known defoamers.

[0049] [Method for supplying alkaline treatment solution] As for the method of supplying the alkaline treatment solution, there are no particular limitations as long as the alkaline treatment solution can come into contact with the pattern obtained in the developing step. For example, the alkaline treatment solution can be supplied to the pattern obtained in the developing step. As for the above-mentioned supply method, there are no particular limitations. There are methods such as immersing the substrate in the alkaline treatment solution, supplying the substrate based on swirling immersion (liquid tray), supplying the alkaline treatment solution to the substrate in the form of spraying, and continuously supplying the alkaline treatment solution to the substrate by means of a mechanism such as a straight nozzle. From the perspectives of the permeability of the alkaline treatment solution to the image area, the removal of the alkaline solution from the non-image area, and manufacturing efficiency, there are methods for supplying the alkaline treatment solution using spray nozzles, straight nozzles, spray nozzles, etc. The method of continuous supply using nozzles is better. From the perspective of the permeability of the alkaline treatment solution to the image area, the method of keeping the alkaline treatment solution supplied by the nozzle on the substrate is better. The above-mentioned methods for supplying alkaline treatment solutions can be used simultaneously (e.g., a combination of supply based on swirling immersion and supply based on spraying, or supply based on swirling immersion and supply based on straight nozzles). For example, immersion feeding allows the treatment solution to easily penetrate after the membrane expands, while spray feeding or mist feeding can improve the removal of non-image areas. Furthermore, the alkaline treatment solution can be used as at least one of the methods used simultaneously. In this invention, it can be configured such that a treatment solution not containing alkali and alkali-generating agents (e.g., the rinsing solution in other rinsing steps described later) is supplied to the pattern (e.g., after the rinsing solution is supplied to the pattern to clean it in other rinsing steps described later), followed by a treatment step based on the alkaline treatment solution. The preferred configuration of the treatment solution not containing alkali and alkali-generating agents is the same as the preferred configuration of the rinsing solution in other rinsing steps described later. There are no particular limitations on the method of supplying the treatment liquid, which does not contain alkali and alkali generating agent, to the pattern in the above-mentioned state, but a supply based on tumble soaking can be cited as an example. There are no particular limitations on the method of supplying the alkaline treatment solution to the pattern as described above, but preferred examples include supply based on spraying and supply based on a straight nozzle. It is believed that by immersing the sample in a non-alkali-containing treatment solution, at least one compound selected from the group consisting of alkali and alkali-generating agents, including those supplied after pattern expansion, can easily penetrate into the pattern, thereby more easily achieving effects such as increased elongation at break. Furthermore, by supplying the alkaline treatment solution through spraying, straight nozzles, etc., the removal (rinsing) of developing residues is sometimes excellent. Furthermore, as a method for supplying the alkaline treatment solution in the processing steps, steps such as continuously supplying the alkaline treatment solution to the substrate, keeping the alkaline treatment solution in a substantially static state on the substrate, vibrating the alkaline treatment solution on the substrate using ultrasound or the like, and combinations thereof can be employed. Among these, the step of supplying or continuously supplying an alkaline treatment solution to the developed pattern by spraying is preferred. Furthermore, it is preferable that the development step is performed by immersion development, and that at least one supply of the alkaline treatment solution in the processing step is performed by continuous supply based on spraying or by a straight nozzle. Based on the above, it is believed that by immersion development, the pattern expands, making it easier for at least one compound selected from the group including alkali and alkali generating agents in the alkaline treatment solution to penetrate into the pattern, thereby more easily obtaining effects such as improved elongation at break.

[0050] The processing time in the processing step (i.e., the time during which the alkaline treatment solution comes into contact with the above-mentioned pattern) is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular requirement for the temperature of the alkaline treatment solution during the processing step, but it is preferably carried out at 10 to 45°C, and more preferably at 18°C ​​to 30°C.

[0051] <Other rinsing steps> The method for manufacturing the hardened material of the present invention may further include a rinsing step (hereinafter also referred to as "other rinsing steps") of rinsing the pattern (the pattern obtained by the developing step) with a rinsing solution that does not contain any of the alkali and alkali generating agents. The rinsing step can be included, for example, before the above-described processing steps and after the above-described developing steps. As the rinsing fluid in the rinsing step, a liquid identical to the alkaline treatment fluid described above can be used, except that it does not contain alkali and alkali generating agent. The preferred state of each component contained in the rinsing fluid is the same as that of each component contained in the alkaline treatment fluid described above, except that it does not contain alkali and alkali generating agent. Furthermore, the rinsing solution can be supplied to the pattern using the same method as the alkaline treatment solution described above.

[0052] <Heating Steps> The pattern obtained by the developing step (the pattern after the processing step) is used in the heating step of heating the pattern obtained by the above developing step. That is, the method for manufacturing the hardened material of the present invention includes a heating step, which heats the pattern obtained by the developing step. Furthermore, the method for manufacturing the hardened material of the present invention may include a heating step, which heats a pattern obtained by other methods without a developing step or a film obtained by a film forming step. During the heating step, resins such as polyimide precursors are cyclized to form resins such as polyimide. Furthermore, it can also perform crosslinking of unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins. The preferred heating temperature (maximum heating temperature) in the heating step is 50~450℃, more preferably 160~250℃, and further preferably 150~230℃. To suppress wafer or panel warping, heating at a low temperature is preferred, with the preferred heating temperature (maximum heating temperature) being 150~200℃, more preferably 150~190℃, and further preferably 150~180℃.

[0053] The heating step is preferably a step in which the polyimide precursor is promoted within the pattern by heating using the action of at least one compound selected from the group consisting of the above-mentioned base and bases generated from the above-mentioned base generating agent.

[0054] Regarding the heating process, it is preferable to increase the temperature at a rate of 1 to 12°C per minute from the initial temperature to the maximum heating temperature. A rate of 2 to 10°C per minute is more preferred, and 3 to 10°C per minute is even more preferable. By setting the heating rate to 1°C per minute or higher, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C per minute or lower, residual stress in the hardened material can be mitigated. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0055] The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the heating process begins and reaches the maximum heating temperature. For example, in the case of applying the resin composition of the present invention to a substrate and then drying it, the temperature of the dried film (layer) is preferred, for example, starting the heating process from a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0056] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0057] In particular, when forming a multilayered body, from the viewpoint of interlayer tightness, a heating temperature of 30°C or above is preferred, 80°C or above is even better, 100°C or above is further preferred, and 120°C or above is especially preferred. The upper limit of the above heating temperature is preferably below 350°C, even better below 250°C, further better below 240°C, and best below 230°C. It can also be set to below 200°C.

[0058] Heating can be performed in stages. For example, the following steps can be performed: increasing the temperature from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, and then increasing the temperature from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9,159,547, it is preferable to perform the treatment while irradiating the membrane with ultraviolet light. This pretreatment step can improve the membrane's properties. The pretreatment step can be performed in a short time, approximately 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferred. The pretreatment can be performed in two or more stages; for example, the first stage of pretreatment can be performed in the range of 100–150°C, followed by the second stage of pretreatment in the range of 150–200°C. Furthermore, cooling can be performed after heating, and a cooling rate of 1~5℃ / minute is preferred at this time.

[0059] In terms of preventing the decomposition of certain resins, it is preferable to conduct the heating process in a low-oxygen environment by passing inert gases such as nitrogen, helium, or argon through the heating step and performing the process under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even better. There are no particular limitations on the heating mechanism used in the heating process; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0060] <Post-development exposure steps> In addition to the heating step mentioned above, the pattern obtained by the development step (the pattern after the processing step) can also be used in the post-exposure step of the pattern after the exposure and development step. That is, the method for manufacturing the hardened material of the present invention may include a post-development exposure step, which exposes the pattern obtained by the development step. In the post-development exposure step, it can promote, for example, the cyclization reaction of polyimide precursors by photoalkali generating agents or the removal of acid-degrading groups by photoacid generating agents. In the post-development exposure step, it is sufficient to expose at least a portion of the pattern obtained in the development step, but it is preferable to expose the entire pattern. The exposure amount in the post-development exposure step is preferably 50~20,000 mJ / cm², and even better if the exposure energy is converted to the wavelength at which the photosensitive compound is sensitive. The post-development exposure step can be performed using the light source described in the above exposure step, with broadband light being preferable.

[0061] <Metal Layer Formation Steps> The pattern obtained by the developing step (preferably a pattern for the heating step) can be used in the metal layer forming step of forming a metal layer on the pattern. That is, the method for manufacturing the hardened material of the present invention preferably includes a metal layer forming step, which forms a metal layer on a pattern obtained by the developing step (preferably a pattern for the heating step).

[0062] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are preferred, with copper being even more preferred.

[0063] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), stripping, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited. As a preferred example of electroplating, electrolytic plating using copper sulfate or copper cyanide plating solutions can be cited.

[0064] For the thickness of the metal layer, a thickness of 0.01~50μm is preferred, and 1~10μm is even better.

[0065] <Applications> Examples of applications applicable to the manufacturing method of the cured material of the present invention or to the cured material of the present invention include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and stress-relief films. Other examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed by etching insulating films used in practical mounting applications as described above. For these applications, please refer to, for example, Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimide,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and Japan Polyimide / Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0066] Furthermore, the method for manufacturing the cured material of the present invention or the cured material of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, in the application of etching forming components, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0067] (Laminated bodies and methods for manufacturing laminated bodies) The laminate of the present invention refers to a structure having a plurality of layers formed by the hardening material of the present invention. The laminate of the present invention is a laminate comprising two or more layers formed of a hardened material, and may also be a laminate consisting of three or more layers. In the above-mentioned laminate, at least one of the two or more layers formed by the hardener is formed by the hardener of the present invention. From the viewpoint of suppressing the shrinkage of the hardener or the deformation of the hardener accompanying the shrinkage, it is also preferable that all the layers formed by the hardener in the above-mentioned laminate are formed by the hardener of the present invention.

[0068] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the hardened material of the present invention, and it is even more preferable to include repeating the steps of the method for manufacturing the laminate of the present invention a plurality of times.

[0069] The laminate of the present invention comprises two or more layers formed of a hardened material, and it is preferable that a metal layer is included between any one of the aforementioned layers formed of the hardened material. Regarding the aforementioned metal layer, it is preferable that it is formed by the aforementioned metal layer forming step. That is, the method for manufacturing the laminate of the present invention further includes, preferably, a metal layer forming step, in which a metal layer is formed on the layer formed by the hardened material during a plurality of processes of manufacturing the hardened material. The preferred form of the metal layer forming step is as described above. As an example of the aforementioned laminate, a laminate structure comprising at least three layers stacked sequentially: a first layer formed of a hardener, a metal layer, and a second layer formed of a hardener is preferred. Preferably, both the first layer formed by the cured material and the second layer formed by the cured material are layers formed by the cured material of the present invention. The resin composition of the present invention used to form the first layer formed by the cured material and the resin composition of the present invention used to form the second layer formed by the cured material can have the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0070] <Layering Steps> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination process includes a series of steps performed sequentially 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) processing step, and (e) heating step. Alternatively, steps (a) film formation step and (d) heating step may be repeated. Furthermore, after step (e) heating step, step (f) metal layer formation step may be included. Also, after the heating step, the aforementioned post-development exposure step may be included. It goes without saying that the aforementioned drying step can be appropriately included in the lamination process.

[0071] If a further deposition step is performed after the deposition step, a surface activation treatment step can be performed after the aforementioned exposure step, the aforementioned heating step, or the aforementioned metal layer formation step. Plasma treatment can be exemplified as a surface activation treatment. Details of the surface activation treatment will be described later.

[0072] It is preferable to perform the above-mentioned layering steps 2 to 20 times, and even better to perform them 2 to 9 times. For example, in a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer configuration, it is preferable to have 2 or more resin layers and 20 or fewer resin layers, and it is even more preferable to have 2 or more resin layers and 9 or fewer resin layers. The composition, shape, and film thickness of the above layers can be the same or different.

[0073] In this invention, it is particularly preferred that the cured resin composition (resin layer) of the present invention is formed by further covering the metal layer after the metal layer is formed. Specifically, examples include repeating the following steps in sequence: (a) film formation, (b) exposure, (c) development, (d) processing, (e) heating, and (f) metal layer formation; or repeating the following steps in sequence: (a) film formation, (d) heating, and (e) metal layer formation. By alternately performing the deposition steps of the resin composition layer (resin layer) and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be deposited alternately.

[0074] (Surface activation treatment step) The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step can also be performed after the surface activation treatment step of the resin composition layer, after the development step described above. Regarding the surface activation treatment, it can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. It is preferable to perform surface activation treatment on at least a portion of the metal layer, and it is preferable to perform surface activation treatment on a portion or all of the region of the metal layer on which the resin composition layer is formed. Thus, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved. Furthermore, it is preferable to perform surface activation treatment on part or all of the exposed resin composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the resin composition layer, the adhesion between the resin layer and the metal layer disposed on the surface-activated surface can be improved. In particular, in cases where the resin composition layer hardens due to negative development, it is less susceptible to damage from the surface treatment, thereby easily improving adhesion. As a surface activation treatment, specifically, plasma treatment, corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, etc., selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixture, argon / oxygen mixture, etc.), surface treatment based on ultraviolet (UV) ozone method, immersion treatment in hydrochloric acid aqueous solution to remove oxide film followed by immersion in an organic surface treatment agent containing a compound having at least one amine group and a thiol group, and mechanical roughening treatment using a brush are preferred, especially oxygen plasma treatment using oxygen as the raw material gas. In the case of corona discharge treatment, an energy of 500~200,000 J / m2 is preferred, 1000~100,000 J / m2 is more preferred, and 10,000~50,000 J / m2 is optimal.

[0075] (Semiconductor device manufacturing methods) This invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured material of this invention or a method for manufacturing a multilayer of this invention. For specific examples of semiconductor devices in which the resin composition of this invention is used in the formation of an interlayer insulating film for a redistribution layer, please refer to paragraphs 0213-0218 of Japanese Patent Application Publication No. 2016-027357 and Figure 1, and these contents are incorporated herein by reference.

[0076] (Photosensitive resin composition) The photosensitive resin composition is the photosensitive resin composition used in the manufacturing method of the cured material of the present invention, the manufacturing method of the laminate of the present invention, or the manufacturing method of the semiconductor element of the present invention. The photosensitive resin composition of the present invention comprises a polyimide precursor having repeating units represented by formula (2) and a photopolymerization initiator. The following describes in detail the components contained in the photosensitive resin composition of the present invention.

[0077] <Specific Resin> The photosensitive resin composition contains a polyimide precursor (specific resin) having repeating units represented by formula (2). Furthermore, it is preferable for a particular resin to have polymerizable groups, and even more preferable if it contains free radical polymerizable groups. In cases where a particular resin has free radical polymerizable groups, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later, and it is even more preferable that it includes both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Furthermore, depending on the need, it can include the sensitizer described later. Such resin compositions of the present invention can be used to form, for example, negative photosensitive films. Furthermore, certain resins may possess polar conversion groups such as acid-decomposing groups. In cases where a particular resin has acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid-generating agent described later. Such resin compositions of the present invention can be used to form, for example, chemically amplified positive or negative photosensitive films.

[0078] [Polyimide precursor] The polyimide precursor used in this invention comprises repeating units represented by the following formula (2). [Chemical Formula 2] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 independently represent a monovalent organic group.

[0079] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, with oxygen atoms being preferred. In formula (2), R 111 represents a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, preferably including straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof, with groups comprising aromatic groups with 6 to 20 carbon atoms being more preferred. The aforementioned straight-chain or branched aliphatic groups can be substituted with groups whose hydrocarbon groups in the chain contain heteroatoms, and the aforementioned cyclic aliphatic groups and aromatic groups can be substituted with groups whose cyclic hydrocarbon groups contain heteroatoms. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, particularly those represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is a group comprising a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

[0080] R 111 is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more may be used. Specifically, diamines comprising aliphatic groups with 2 to 20 carbon atoms (either straight or branched), cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof, are preferred; diamines comprising aromatic groups with 6 to 20 carbon atoms are even more preferred. The aforementioned straight or branched aliphatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the chain, and the aforementioned cyclic aliphatic and aromatic groups can be substituted with groups containing heteroatoms in the hydrocarbon group of the ring. Examples of groups comprising aromatic groups are given below.

[0081]

Chemical Formula 3

[0082] As a diamine, specifically, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diamine 3,3'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ketone or 3,3'-diaminodiphenyl ketone, 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) arsenide, bis(4-amino-3-hydroxyphenyl) arsenide, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] arsenide, bis[4-(3-aminophenoxy)phenyl] arsenide, bis[4-(2-aminophenoxy)phenyl] arsenide, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl arsenide, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonate, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-Diaminophen, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2- bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl At least one diamine selected from the following: 3,4'-amino-2-trifluoromethylphenoxy)diphenyl benzoyl, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl benzoyl, 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'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0083] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0084] Alternatively, it can be preferably used as a diamine having two or more alkyl diol units as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 on the main chain.

[0085] From the viewpoint of the flexibility of the obtained organic membrane, R 111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a group including an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably phenyl, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO 2-. Here, the aliphatic hydrocarbon group is preferably alkyl. Ar being phenyl and L being -O- is further preferred.

[0086] Furthermore, from the viewpoint of i-ray transmittance, it is preferable that R 111 is a divalent organogroup represented by formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organogroup represented by formula (61) is more preferable. Equation (51) [Chemical Formula 4] In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoromethyl group. * represents the bonding site with the nitrogen atom in formula (2). Examples of monovalent organic groups in R 50 to R 57 include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [Chemical Formula 5] In formula (61), R 58 and R 59 are fluorine atoms, methyl or trifluoromethyl atoms, respectively, and * represents the bonding sites with nitrogen atoms in formula (2). Examples of diamines providing the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used in combination.

[0087] In formula (2), R 115 represents a tetravalent organogroup. As a tetravalent organogroup, a tetravalent organogroup containing an aromatic ring is preferred, and the group represented by formula (5) or formula (6) below is even more preferred. In formula (5) or formula (6), * independently represents the bonding site with other structures.

Chemical Formula 6

[0088] Specifically, R115 can be exemplified by the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride. As the structure corresponding to R115, the polyimide precursor may contain only one type of tetracarboxylic acid dianhydride residue, or it may contain two or more types. For example, from the viewpoint of elongation at break and adhesion to metal or resin layers, it is also better for a polyimide precursor to contain a structure in which R115 is represented by the above formula (5) and R112 is a single bond and R112 is -O-. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 7] In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.

[0089] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Alkane dianhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrides, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydrides, 1,4,5,6-naphthalenetetracarboxylic acid dianhydrides, 2,2',3,3'-diphenyltetracarboxylic acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,2,4,5-naphthalenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and such alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0090] Alternatively, the tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as a better example.

[0091] In formula (2), R 113 and R 114 each independently represent a monovalent organic group. Preferably, the monovalent organic group comprises a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R 113 and R 114 comprises a polymerizable group, and even more preferable that both comprise polymerizable groups. It is also preferable that at least one of R 113 and R 114 comprises two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxybutyl, benzoxazole, block isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having vinyl unsaturated bonds is preferred. Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with the group represented by formula (III) below being preferred.

[0092] [Chemical Formula 8]

[0093] In formula (III), R 200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred. In equation (III), * indicates the bonding site with other structures. In formula (III), R 201 represents a alkyl group with 2 to 12 carbon atoms, -CH 2CH(OH)CH 2-, cycloalkyl group or polyalkylene group. Examples of preferred R 201 include alkylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH 2CH(OH)CH 2-, polyalkylene, alkylene, propylene, -CH 2CH(OH)CH 2-, cyclohexylene, polyalkylene, and alkylene, propylene, or polyalkylene are preferred, with alkylene, propylene, or polyalkylene being further preferred. In this invention, polyalkylene oxide refers to an alkylene oxide group directly bonded to two or more groups. The alkylene groups in the plurality of alkylene oxide groups contained in the polyalkylene oxide group may be the same or different.

[0094] In formula (2), at least one of R 113 and R 114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, there is no particular limitation as long as it is a base-soluble group such as a phenolic hydroxyl group or a carboxyl group that decomposes under the action of acid. However, acetal, ketal, silyl alkyl, silyl ether, and tertiary alkyl ester groups are preferred. From the point of view of exposure sensitivity, acetal or ketal groups are more preferred. Specific examples of acid-degrading groups include tributoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tributoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0095] Furthermore, it is preferable that the polyimide precursor contains fluorine atoms in its structure. A fluorine atom content of 10% by mass or more, and less than 20% by mass, is preferred in the polyimide precursor.

[0096] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0097] It is preferable that the repeating unit represented by formula (2) is the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in this invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the width of the exposure latitude can be increased. Equation (2-A) [Chemical Formula 9] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 independently represent divalent organic groups, R113 and R114 independently represent monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group, preferably both of which are groups containing polymerizable groups.

[0098] A1, A2, R111, R113 and R114 have the same meaning as A1, A2, R111, R113 and R114 in equation (2), and the preferred range is also the same. R 112 has the same meaning as R 112 in equation (5), and the preferred range is also the same.

[0099] Polyimide precursors may contain one repeating unit represented by formula (2), or two or more repeating units. They may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it is self-evident that polyimide precursors may contain other types of repeating units besides the repeating unit of formula (2) mentioned above.

[0100] As one embodiment of the polyimide precursor in this invention, an example is provided where the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is preferred, 90 mol% or more is further preferred, and more than 90 mol% is especially preferred. There is no particular limitation on the upper limit of the total content; all repeating units in the polyimide precursor, except for the terminal units, can also be the repeating units represented by formula (2).

[0101] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the aforementioned polyimide precursor only needs to be 1.0 or higher. Furthermore, there is no particular upper limit for the molecular weight dispersion of the polyimide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is even better, and 6.0 or lower is further preferred. In this specification, the molecular weight dispersion is a value calculated using the weight average molecular weight / number average molecular weight. Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are within the aforementioned ranges.

[0102] -End- Capping Agent- In methods for manufacturing polyimide precursors, etc., it is preferable to seal the carboxylic anhydride, anhydride derivatives, or amine groups remaining at the resin ends of the polyimide precursor, etc., to further improve storage stability. When sealing the carboxylic anhydride and anhydride derivatives remaining at the resin ends, monohydric alcohols, phenols, thiols, benzenethiophenols, monoamines, etc., can be used as sealing agents. From the viewpoint of reactivity and film stability, monohydric alcohols, phenols, or monoamines are preferred. Preferred compounds as monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tertiary alcohols such as butanol and adamantanol. Preferred compounds among phenols include phenols, methoxyphenols, methylphenols, naphth-1-ols, naphth-2-ols, and hydroxystyrene. Preferred compounds among monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, and by reacting multiple end-capping agents, multiple different end groups can be introduced. Furthermore, when sealing the amine groups at the end of the resin, compounds with functional groups capable of reacting with the amine groups can be used for sealing. Preferred sealants for amine groups include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norcamphene-2,3-dicarboxylic anhydride. Furthermore, preferred compounds as carboxylic acid chlorides include acetyl chloride, acrylamide chloride, propionyl chloride, methacrylamide chloride, trimethylacetyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamic acid chloride, 1-adamantanemethyl chloride, heptafluorobutyric acid chloride, stearic acid chloride, and benzyl chloride.

[0103] -Solid precipitation- In the manufacture of polyimide precursors, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer components are added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, causing the polymer components to precipitate as a solid and then dried, thereby obtaining the polyimide precursor. To improve the purification degree, the operations of re-dissolving, re-precipitating, and drying the polyimide precursor may be repeated. Furthermore, a step of using an ion exchange resin to remove ionic impurities may be included.

[0104] 〔content〕 The content of a specific resin in the resin composition of the present invention is preferably 20% by mass or more relative to the total solid content of the resin composition, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The resin composition of the present invention may contain only one specific resin, or it may contain two or more resins. When two or more resins are contained, it is preferable that the total amount is within the above-mentioned range.

[0105] Furthermore, it is preferable that the resin composition of the present invention contains at least two resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or it may contain two or more specific resins, but it is preferred to contain two or more specific resins. In the case where the resin composition of the present invention contains two or more specific resins, it is preferable to contain two or more polyimide precursors that are polyimide precursors and are derived from different structures of dianhydrides (R 115 described in formula (2) above). For example, from the viewpoint of elongation at break and adhesion to the metal or resin layer, it is preferable to have a polyimide precursor having a structure in which R115 is represented by the above formula (5) and R112 is a single bond, and a polyimide precursor having a structure in which R115 is represented by the above formula (5) and R112 is -O-.

[0106] <Other Resins> The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins"). Other resins include polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, resins containing polysiloxane or siloxane structures, (meth)acrylic resin, (meth)acrylic acid amide resin, ethyl carbamate resin, butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a (meth)acrylic resin with a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻³ moles / g or more) with a weight average molecular weight of 50,000 or less can be added to the resin composition, thereby improving the coatability of the resin composition, the solvent resistance of the pattern (cured material), etc.

[0107] When the resin composition of the present invention includes other resins, it is preferable that the content of other resins is 0.01% by mass or more relative to the total solid content of the resin composition, more preferably 0.05% by mass or more, further 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. Furthermore, it is preferable that the content of other resins in the resin composition of the present invention is 30% by mass or less relative to the total solid content of the resin composition, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When two or more other resins are contained, it is preferable that the total amount is within the above-mentioned range.

[0108] [Photopolymerization initiator] The photosensitive resin composition contains a photopolymerization initiator. Photopolymerization initiators are preferably photoradical polymerization initiators. There are no particular limitations on the photoradical polymerization initiator; it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are photosensitizing to light in the ultraviolet to visible regions are preferred. Alternatively, it can be an activator that interacts with a photoexcited sensitizer to generate active free radicals.

[0109] The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L / mol⁻¹ / cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using a UV-Vis spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0110] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a trihalomethyl skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron-aromatic complexes, etc. For details regarding these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference. Furthermore, examples can be cited in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peracid-based initiators described in Japanese Patent Application Publication No. 2019-167313, and these contents are also incorporated into this specification.

[0111] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611 can be cited, and this content is incorporated into this specification. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0112] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and this content is incorporated into this specification.

[0113] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0114] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0115] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used, and this content is included in this specification.

[0116] Examples of phosphine oxide initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

[0117] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0118] Oxime compounds are a better example of photoradical polymerization initiators. By using oxime compounds, exposure latitude can be improved more effectively. Oxime compounds have a wider exposure latitude (exposure margin) and also act as photocuring accelerators, making them particularly advantageous.

[0119] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0120] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoxyloxy(imino))butane-2-one, 3-(acetoxy(imino))butane-2-one, 3-(propoxy(imino))butane-2-one, 2-(acetoxy(imino))pentane-3-one, 2-((acetoxy)imino)-1-phenylpropane-1-one, 2-(benzoxyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonoxy)imino)butane-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linker within the molecule.

[0121]

Chemical Formula 10

[0122] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, the photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structures can also be used.

Chemical Formula 11

[0123] Oxime compounds having a cyclohexane ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, and these contents are incorporated into this specification.

[0124] As a photoradical polymerization initiator, oxime compounds having at least one benzene ring in the carbazole ring as the naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0125] Furthermore, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, and these contents are included in this specification.

[0126] Nitro-containing oxime compounds can be used as photopolymerization initiators. It is also preferable that the nitro-containing oxime compound is a dimer. Specific examples of nitro-containing oxime compounds include the compounds described in paragraphs 0031-0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008-0012 and 0070-0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007-0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) can also be cited as a nitro-containing oxime compound.

[0127] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0128] As a photoradical polymerization initiator, oxime compounds obtained by bonding hydroxyl groups to the carbazole backbone can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, and this content is included in this specification.

[0129] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group Ar OX1 with an electron-withdrawing group introduced onto the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic Ar OX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred for the ease of forming a film with excellent lightfastness, with benzoyl being even more preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthio, arylthio, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthio, arylthio or amino are even more preferred, and alkoxy, alkylthio or amino are further preferred.

[0130] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and formula (OX2), with the compound represented by formula (OX2) being more preferred.

Chemical Formula 12

[0131] In the above formula, it is preferable that RX12 is an electron-withdrawing group, and RX10, RX11, RX13, and RX14 are hydrogen atoms.

[0132] As a specific example of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 are cited, and this content is incorporated into this specification.

[0133] Examples of optimal oxime compounds include those with specific substituents as shown in Japanese Patent Application Publication No. 2007-269779 or those with thioaryl groups as shown in Japanese Patent Application Publication No. 2009-191061, and these are included in this specification.

[0134] From the perspective of exposure sensitivity, photoradical polymerization initiators are preferably compounds selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetylsphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0135] A further preferred photoradical polymerization initiator is a trihalomethane trihalomethane compound, an α-aminoketone compound, an acetophosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, preferably selected from at least one compound selected from the group consisting of trihalomethane trihalomethane compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds, and even more preferably, a metallocene compound or an oxime compound is used.

[0136] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by cyclization of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; and benzyl derivatives such as benzyl dimethyl ketal. Additionally, compounds represented by formula (I) below can also be used.

[0137]

Chemical Formula 13

[0138] In formula (I), RI00 is an alkyl group with 1 to 20 carbon atoms, an alkyl group with 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbon atoms or a phenyl group, or an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group with 2 to 12 carbon atoms, an alkyl group with 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group with 1 to 4 carbon atoms, at least one of which is a phenyl or biphenyl group. RI01 is a group represented by formula (II) or a group that is the same as RI00. RI02 to RI04 are each independently an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms or a halogen atom.

[0139]

Chemical Formula 14

[0140] In the formula, R I05~R I07 are the same as R I02~R I04 in the above formula (I).

[0141] Furthermore, the photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, and this content is incorporated into this specification.

[0142] As photoradical polymerization initiators, difunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and ( ) described in Japanese Patent Application Publication No. 2013-522445. G) Cmpd1-7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators as described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) as described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent No. 6469669, etc., and these contents are incorporated into this specification.

[0143] The content of the photopolymer initiator relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount within the above-mentioned range is preferred. Furthermore, photopolymerization initiators sometimes also function as thermal polymerization initiators, and therefore crosslinking based on photopolymerization initiators can sometimes be further carried out by heating in an oven or heating plate.

[0144] [Sensitizer] The resin composition may include sensitizers. Sensitizers absorb specific active radiation to become electronically excited. These electronically excited sensitizers then come into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., thereby generating electron transfer, energy transfer, and heat generation. Consequently, the thermal free radical polymerization initiators and photofree radical polymerization initiators undergo chemical changes and decompose, generating free radicals, acids, or bases. As usable sensitizers, compounds such as ethanolamine, benzophenone, milchnerone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazole azomethine, phthalocyanine, benzopyran, and indigo can be used. Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallyl dihydroindone, and p-dimethylamino Benzylene dihydroindone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3-ethoxy 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamine Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoaniline, N-methylacetamide, 3',4'-dimethylacetamide, etc. Among these, from the viewpoint of elongation at break and adhesion to metal or resin layers, compounds with an ethanolamine structure or a coumarin structure are preferred, with N-phenyldiethanolamine or (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester) being even more preferred. Alternatively, other sensitizing pigments can be used. For details regarding the sensitized pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, and this information is incorporated into this specification.

[0145] When the resin composition contains a sensitizer, the sensitizer content relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass. A single sensitizer may be used, or two or more may be used simultaneously.

[0146] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO₂-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithioaminocarbamate, and xanthate compounds having a thiocarbonyl sulfide group for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0147] Furthermore, the chain transfer agent may also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, and this content is incorporated into this specification.

[0148] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids content of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content is within the above-mentioned range.

[0149] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator is a compound that produces at least one of Bristol acid and Lewis acid upon irradiation with light in the range of 200 nm to 900 nm. The irradiated light is preferably light with a wavelength of 300 nm to 450 nm, and more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator capable of producing acid upon photosensitization is preferred. Examples of acids produced include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, monophosphate esters, diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonic acid amides.

[0150] Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organohalides, organoborates, disulfonic acid compounds, and onium salts. From the perspective of sensitivity and storage stability, organohalogen compounds, oxime sulfonates, and onium salts are preferred; from the perspective of the mechanical properties of the formed film, oxime esters are preferred.

[0151] Examples of quinone diazide compounds include those obtained by attaching a sulfonate bond of quinone diazide to a monovalent or polyvalent hydroxyl group, those obtained by attaching a sulfonamide bond of quinone diazide to a monovalent or polyvalent amine group, and those obtained by attaching a sulfonate bond and / or a sulfonamide bond of quinone diazide to a polyhydroxy polyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinone diazide, but it is preferable that at least 40 moles of the total functional groups are substituted with quinone diazide. By containing such a quinone diazide compound, a resin composition capable of photosensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from a typical ultraviolet mercury lamp can be obtained.

[0152] Specifically, examples of hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tributanol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, and BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (These are product names, Honshu) The products manufactured by Chemical Industry Co., Ltd. include BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), phenolic varnish resins, etc., but are not limited to these.

[0153] Examples of amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, etc., but are not limited to these.

[0154] Furthermore, examples of polyhydroxy polyamine compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited to these.

[0155] Among these, compounds containing phenolic compounds and esters with 4-naphthoquinone diazidesulfonyl groups are preferred as quinone diazide compounds. This allows for higher sensitivity and higher resolution to i-ray exposure.

[0156] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by weight, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin. By setting the content of the quinone diazide compound within this range, the contrast between the exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is therefore preferable. Furthermore, sensitizers or the like can be added as needed.

[0157] It is preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compound"). There are no particular restrictions on the presence of an oxime sulfonate group in oxime sulfonate compounds, but oxime sulfonate compounds represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) are preferred.

[0158]

Chemical Formula 15

[0159] In formula (OS-1), X3 represents an alkyl, alkoxy, or halogen atom. When multiple X3s are present, they may be the same or different. The alkyl and alkoxy atoms in X3 may have substituents. As the alkyl group in X3, a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in X3, a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in X3, a chlorine or fluorine atom is preferred. In equation (OS-1), m3 represents an integer from 0 to 3, with 0 or 1 being preferred. When m3 is 2 or 3, the complex number of X3 can be the same or different. In formula (OS-1), R 34 represents an alkyl or aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group that can be substituted with W, a naphthyl group that can be substituted with W, or an anthracene group that can be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloaryl group having 6 to 20 carbon atoms.

[0160] In formula (OS-1), m3 is 3, X3 is methyl, X3 is substituted at the ortho position, and R34 is preferably a straight-chain alkyl group with 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonormethylmethyl or p-tolyl.

[0161] As specific examples of oxime sulfonate compounds represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Application Publication No. 2015-194674 are examples, and such contents are incorporated into this specification.

[0162] [Chemical Formula 16]

[0163] In formulas (OS-103) to (OS-105), Rs1 represents alkyl, aryl, or heteroaryl; sometimes there are multiple Rs2 that independently represent hydrogen atoms, alkyl, aryl, or halogen atoms; sometimes there are multiple Rs6 that independently represent halogen atoms, alkyl, alkoxy, sulfonic acid, aminosulfonyl, or alkoxysulfonyl; Xs represents O or S; ns represents 1 or 2; and ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbons), aryl group (preferably with 6 to 30 carbons), or heteroaryl group (preferably with 4 to 30 carbons) represented by R s1 may have known substituents within the range that can achieve the effects of the present invention.

[0164] In formulas (OS-103) to (OS-105), Rs2 is preferably a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms), or an aryl group (preferably with 6 to 30 carbon atoms), with hydrogen or alkyl being more preferred. In compounds where two or more Rs2 are present, it is preferred that one or two are alkyl, aryl, or halogen atoms, more preferred that one is alkyl, aryl, or halogen atom, and particularly preferred that one is alkyl and the remainder are hydrogen atoms. The alkyl or aryl group represented by Rs2 may have known substituents within the range that allows the effects of the present invention to be obtained. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, with O being preferred. In formulas (OS-103) to (OS-105) above, a ring containing Xs as a member is a 5-member ring or a 6-member ring.

[0165] In equations (OS-103) to (OS-105), ns represents 1 or 2. When Xs is 0, ns is better if it is 1, and when Xs is S, ns is better if it is 2. In formulas (OS-103) to (OS-105), the alkyl group (preferably with 1 to 30 carbon atoms) and alkoxy group (preferably with 1 to 30 carbon atoms) represented by R s6 may have substituents. In equations (OS-103) to (OS-105), ms represents an integer from 0 to 6, an integer from 0 to 2 is preferred, 0 or 1 is even better, and 0 is the best.

[0166] Furthermore, the compound represented by the above formula (OS-103) is preferably represented by the compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is preferably represented by the compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is preferably represented by the compound represented by the following formula (OS-108) or formula (OS-109).

Chemical Formula 17

[0167] In formulas (OS-106) to (OS-111), Rt1 represents alkyl, aryl, or heteroaryl; Rt7 represents a hydrogen atom or a bromine atom; Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl; Rt9 represents a hydrogen atom, a halogen atom, methyl, or methoxy; and Rt2 represents a hydrogen atom or a methyl group. In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, with hydrogen atom being preferred.

[0168] In formulas (OS-106) to (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. It is preferred that the alkyl group has 1 to 8 carbon atoms, a halogen atom, or a phenyl group has 1 to 8 carbon atoms, even more preferred, and a alkyl group has 1 to 6 carbon atoms, with methyl being particularly preferred.

[0169] In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with hydrogen atom being preferred. R t2 represents a hydrogen atom or a methyl group, with hydrogen atom being preferred. Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime can be either one or a mixture. As specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 are examples, and such contents are incorporated into this specification.

[0170] Other preferred forms of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

[0171] [Chemical Formula 18]

[0172] In formula (OS-101) or formula (OS-102), Ru9 represents a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acetyl, aminomethyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. It is preferred that Ru9 is cyano or aryl, and it is further preferred that Ru9 is cyano, phenyl, or naphthyl. In formula (OS-101) or formula (OS-102), Ru2a represents alkyl or aryl. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR u5-, -CH 2-, -CR u6H- or CR u6R u7-, and Ru5~R u7 independently represent alkyl or aryl groups.

[0173] In formula (OS-101) or formula (OS-102), Ru1 to Ru4 independently represent hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, amino groups, alkoxycarbonyl groups, alkylcarbonyl groups, arylcarbonyl groups, amide groups, sulfonyl groups, cyano groups, or aryl groups. Two of Ru1 to Ru4 can be bonded together to form a ring. In this case, the ring can undergo ring condensation to form a condensed ring together with the benzene ring. Preferably, hydrogen atoms, halogen atoms, or alkyl groups are used as Ru1 to Ru4, and it is also preferred that at least two of Ru1 to Ru4 are bonded together to form an aryl group. Preferably, all of Ru1 to Ru4 are hydrogen atoms. The above-mentioned substituents may also have substituents.

[0174] The compound represented by formula (OS-101) is preferred over the compound represented by formula (OS-102). Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure of the oxime or benzothiazole ring (E, Z, etc.) can be either one of them or a mixture thereof. As specific examples of compounds represented by formula (OS-101), compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674 are examples, and such contents are incorporated into this specification. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 19] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0175] Alternatively, the following compounds represented by the structural formulas can be cited as better examples.

Chemical Formula 20

[0176] As organohalogenated compounds, examples include Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication Nos. 46-4605, 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, and MP Hutt's "Jurnal of Heterocyclic". The compounds described in Chemistry 1 (No. 3), (1970), etc., are included in this specification. In particular, the trihalomethyl-substituted oxazole compounds: S-trimethyloxazole compounds are preferred examples. More preferably, examples can be given of s-trihalomethane derivatives formed by at least one mono-, di-, or trihalomethane-substituted methyl group bonded to an s-trihalomethane ring. Specifically, examples include 2,4,6-tris(monochloromethyl)-s-trihalomethane, 2,4,6-tris(dichloromethyl)-s-trihalomethane, 2,4,6-tris(trichloromethyl)-s-trihalomethane, 2-methyl-4,6-bis(trichloromethyl)-s-trihalomethane, and 2-n-propyl-4,6-bis(trichloromethyl)-s-trihalomethane. -trichlorophenyl, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-phenyl-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trichlorophenyl, 2-[1-(p-methoxyphenyl) [2-(p-methoxystyryl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris-, 2-styryl-4,6-bis(trichloromethyl)-s-tris-, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-tris-, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-, 2-(4-naphthoxy) Naphthyl)-4,6-bis(trichloromethyl)-s-tris, 2-phenylthio-4,6-bis(trichloromethyl)-s-tris, 2-benzylthio-4,6-bis(trichloromethyl)-s-tris, 2,4,6-tris(dibromomethyl)-s-tris, 2,4,6-tris(tribromomethyl)-s-tris, 2-methyl-4,6-bis(tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

[0177] Examples of organoborate compounds include, for example, Japanese Patent Application Publication No. 62-143044, Japanese Patent Application Publication No. 62-150242, Japanese Patent Application Publication No. 9-188685, Japanese Patent Application Publication No. 9-188686, Japanese Patent Application Publication No. 9-188710, Japanese Patent Application Publication No. 2000-131837, Japanese Patent Application Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Publication No. 2002-116539, etc., and Kunz, Martin, “Rad Tech’98. Proceeding April”. The organoborates described in "Chicago" etc., Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and the organoboron-strontium complexes or organoboron-oxystrontium complexes described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553, and the organoboron-strontium complexes described in Japanese Patent Application Publication Nos. 19-22, 1998, etc. The present specification includes, as specific examples, organoboron-phosphorus complexes described in Japanese Patent Application Publication No. 9-188710, organoboron-transition metal coordination complexes such as those in Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, and Japanese Patent Application Publication No. 7-292014, and such contents.

[0178] Examples of diazonium compounds include compounds described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application Publication No. 2002-1328465, as well as diazonium compounds.

[0179] Examples of the aforementioned onium salt compounds include, for instance, the diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21, 423 (1980); the ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Publication No. 4-365049, etc.; the phosphonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056; the phosphonium salts described in European Patent Nos. 104,143, 339,049, and 410,201; the phosphonium salts described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and the phosphonium salts described in European Patent Nos. 370,693 and 3... The strontium salts described in the specifications of patents 90,214, 233,567, 297,443, 297,442, US patents 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, German patents 2,904,626, 3,604,580, and 3,604,581, and JVCrivello... Selenium salts described in JVCrivello et al., Macromolecules, 10(6), 1307(1977), Polymer Sci., Polymer Chem. Ed., 17, 1047(1979), arsenic salts, pyridinium salts, and other onium salts described in CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), are included in this specification.

[0180] As onium salts, examples of onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited.

Chemical Formula 21

[0181] Specific examples of better photoacid generators include the following.

Chemical Formula 22

Chemical Formula 23

Chemical Formula 24

[0182] The photoacid generator is preferably used at 0.1 to 20% by mass relative to the total solids content of the resin composition, more preferably at 0.5 to 18% by mass, further preferably at 0.5 to 10% by mass, even more preferably at 0.5 to 3% by mass, and even more preferably at 0.5 to 1.2% by mass. A photoacid generator can be used alone or in combination with multiple agents. When multiple agents are used in combination, the total amount is preferably within the range mentioned above. Furthermore, it is better to use it in conjunction with a sensitizer in order to impart photosensitivity to the desired light source.

[0183] Solvent The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, and alcohols.

[0184] 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, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid)). Ethyl esters, etc.), alkyl esters of 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

[0185] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether 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.

[0186] Among the ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydroglucanone are preferred examples.

[0187] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are good examples.

[0188] As a class of urethanes, dimethyl urethane can be cited as a preferred example.

[0189] Among the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-methoxymorpholine, and N-acetymorpholine are considered as preferred choices.

[0190] Among urea compounds, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are considered to be better choices.

[0191] 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 monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, and diacetone alcohol.

[0192] Regarding solvents, from the perspective of improving the properties of the coating surface, it is better to mix two or more forms.

[0193] In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, L-glucanone, and dihydroglucanone, or a mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

[0194] From the viewpoint of coatability, it is preferable to set the solvent content to a total solids concentration of 5-80% by mass in the resin composition of the present invention, more preferably to a concentration of 5-75% by mass, further preferably to a concentration of 10-70% by mass, and even more preferably to a concentration of 20-70% by mass. The solvent content can be adjusted according to the desired coating thickness and coating method.

[0195] The resin composition of the present invention may contain only one solvent or may contain two or more solvents. When containing two or more solvents, it is preferable that their total content falls within the above-mentioned range.

[0196] <Polymerizing compounds> The resin composition of the present invention preferably contains a polymeric compound. Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0197] [Free radical crosslinking agent] The resin composition of the present invention preferably contains a free radical crosslinking agent. Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, the free radical polymerizable group contains an ethylene unsaturated bond. Examples of such ethylene unsaturated bond groups include vinyl, allyl, vinylphenyl, (meth)acryl, maleicadiimino, and (meth)acrylamine groups. Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the groups containing vinyl unsaturated bonds, and (meth)acryl is more preferred from the viewpoint of reactivity.

[0198] Free radical crosslinking agents are preferably compounds with one or more vinyl unsaturated bonds, but compounds with two or more are even more preferred. Free radical crosslinking agents can have three or more vinyl unsaturated bonds. As for the compounds having two or more ethylene unsaturated bonds, compounds having 2 to 15 ethylene unsaturated bonds are preferred, compounds having 2 to 10 ethylene unsaturated bonds are even more preferred, and compounds having 2 to 6 ethylene unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (hardened material), it is also preferable that the resin composition of the present invention contains compounds having two ethylene unsaturated bonds and the aforementioned compounds having three or more ethylene unsaturated bonds.

[0199] The molecular weight of the free radical crosslinking agent is preferably below 2,000, more preferably below 1,500, and even more preferably below 900. The lower limit of the molecular weight of the free radical crosslinking agent is preferably above 100.

[0200] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, it is also preferable to use addition reactions of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl or amino groups, or hydrogen sulfide groups, with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyl groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Additionally, as another example, compounds that replace the aforementioned unsaturated carboxylic acids can be used, such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and such contents are incorporated into this specification.

[0201] Furthermore, it is preferable that the free radical crosslinking agent is a compound with a boiling point of 100°C or higher at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetramethylolethane tri(meth)acrylate, neopentyl tetramethylolethane tetra(meth)acrylate, dinepentyl tetramethylolethane penta(meth)acrylate, dinepentyl tetramethylolethane hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloxypropyl) ether, tri(acryloxyethyl)isocyanurate, glycerol, or trimethylolethane, which are added to polyfunctional alcohols to form ethylene oxide or propylene oxide, followed by (meth)acrylate. Compounds obtained by esterification, such as ethyl aminocarbamates of (meth)acrylate described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth)acrylic acid, and other multifunctional acrylates or methacrylates and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Alternatively, examples include polyfunctional (meth)acrylates obtained by reacting compounds such as glycidyl (meth)acrylate, which have cyclic ether groups and vinyl unsaturated bonds, with polyfunctional carboxylic acids.

[0202] Furthermore, as a preferred free radical crosslinking agent besides the above, compounds having a cycloid and having two or more groups containing ethylene unsaturated bonds, or cardo resins, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, can also be used.

[0203] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can also be used. Additionally, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0204] In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 can also be used more readily, and such contents are incorporated into this specification.

[0205] Furthermore, in Japanese Patent Application Publication No. 10-062986, the following compound, which is described together with specific examples as formula (1) and formula (2), can also be used as a free radical crosslinking agent. This compound is obtained by (meth)acrylate esterification after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0206] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

[0207] As free radical crosslinking agents, dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)) and structures in which the (meth)acrylic groups are linked via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0208] Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four ethynooxy chains) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (difunctional methyl acrylates with four ethoxy chains) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentynooxy chains) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isobutyryloxy chains); ethyl carbamate oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku). Products manufactured by Kyoisha Chemical Co., Ltd. include UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), and BLEMMER PME400 (manufactured by NOF CORPORATION).

[0209] As free radical crosslinking agents, ethyl carbamate acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and ethyl carbamate compounds with an ethylene oxide backbone described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0210] Free radical crosslinking agents can be those containing acid groups such as carboxyl or phosphate groups. It is preferable that the free radical crosslinking agent containing acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. It is even more preferable that the free radical crosslinking agent containing acid groups is formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred is that, in the free radical crosslinking agent containing acid groups formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl tetrol or dinepentyl tetrol. Commercially available examples include, for instance, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., such as M-510 and M-520.

[0211] The preferred acid value of a free radical crosslinking agent containing an acid group is 0.1~300 mg KOH / g, and the particularly preferred acid value is 1~100 mg KOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, the manufacturing process is excellent, and consequently, the developability is excellent. Furthermore, the polymerizability is good. The above acid value is determined according to the description in JIS K 0070:1992.

[0212] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition. As specific compounds, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-hexanediol diacrylate can be used. Ester, 1,6-hexanediol dimethacrylate, dimethyloltricyclodecane dimethacrylate, dimethyloltricyclodecane dimethacrylate, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, cyanuric acid (EO) modified dimethacrylate, cyanuric acid modified dimethacrylate, difunctional acrylates having other ethyl carbamate bonds, and difunctional methacrylates having ethyl carbamate bonds. Two or more of these can be mixed as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain weight of approximately 200. From the viewpoint of suppressing warpage by controlling the elastic modulus of the accompanying pattern (cured material) in relation to the resin composition of the present invention, a monofunctional free radical crosslinking agent can preferably be used as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are n-butyl (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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and alkenyl glycidyl ether. As a monofunctional free radical crosslinking agent, compounds with a boiling point of over 100°C at normal pressure are preferred in order to suppress volatilization before exposure. In addition, as free radical crosslinking agents with two or more functions, examples include allyl compounds such as diallyl phthalate and trimellitic acid triallyl ester.

[0213] In the case of a free radical crosslinking agent, it is preferable that its content relative to the total solids content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is further preferred.

[0214] Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more at the same time, it is better to keep the total dosage within the above range.

[0215] [Other crosslinking agents] It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In this invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. It is preferable that the compound has a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the photosensitive acid generator or photobase generator mentioned above. It is also preferable that the compound has a plurality of reaction groups within the molecule that promote the formation of covalent bonds between the compound and other compounds in the composition or their reaction products by the action of acid or base. It is preferable that the acid or base mentioned above is generated from the photoacid generator or photoalkali generator during the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred. Other crosslinking agents include, for example, compounds having a structure in which hydrogen atoms of the amine groups are replaced by acetoxymethyl, hydroxymethyl, or alkoxymethyl groups by reacting formaldehyde or formaldehyde and alcohol with melamine, glycourea, urea, alkyl urea, benzoguanamine, or other amine-containing compounds. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Alternatively, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used. Crosslinking agents that use melamine as the above-mentioned amine-containing compounds are called melamine-based crosslinking agents; crosslinking agents that use urea, urea, or alkyl urea are called urea-based crosslinking agents; crosslinking agents that use alkyl urea are called alkyl urea-based crosslinking agents; and crosslinking agents that use benzoguanidine are called benzoguanidine-based crosslinking agents. In these embodiments, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and it is even more preferable that it contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0216] As a compound containing at least one of the alkoxymethyl and acetoxymethyl groups of the present invention, examples of compounds in which the alkoxymethyl or acetoxymethyl group is directly substituted on the nitrogen atom or triatom of the aromatic group or the urea structure described below are provided as structural examples. It is preferred that the alkoxymethyl or acetomethyl group in the above compounds has 2 to 5 carbon atoms, 2 or 3 carbon atoms are preferred, and 2 carbon atoms are even more preferred. It is preferable that the total number of alkoxymethyl and aceoxymethyl groups in the above compounds is 1 to 10, more preferably 2 to 8, and especially preferably 3 to 6. The molecular weight of the above-mentioned compounds is preferably below 1500, and 180 to 1200 is preferred.

[0217]

Chemical Formula 26

[0218] R 100 indicates alkyl or acetylated. R101 and R102 each independently represent a monovalent organic group and can bond with each other to form a ring.

[0219] As compounds in which alkoxymethyl or acetomethyl groups are directly substituted on an aromatic group, examples include various compounds of the following general formula.

[0220] [Chemical Formula 27]

[0221] In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl or acetyl group, and R 103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to produce a base-soluble group (e.g., a group that is released under the action of an acid, or a group represented by -C(R 4) 2COOR 5 (R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is released under the action of an acid.)). R 105 independently represents alkyl or alkenyl groups, a, b and c are each 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. Regarding groups that decompose under the action of acid to produce base-soluble groups, groups that are removed under the action of acid, and the R5 in the group represented by -C(R4)2COOR5, examples include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39). In the formula, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can bond together to form a ring. As the aforementioned alkyl group, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 5 carbon atoms are even more preferred. The aforementioned alkyl group can be either straight-chain or branched. As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is even more preferred. The aforementioned cycloalkyl groups can be monocyclic structures or polycyclic structures such as condensed rings. The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and phenyl is even more preferred. Aryl groups with 7 to 20 carbon atoms are preferred, and aryl groups with 7 to 16 carbon atoms are even more preferred. The aforementioned aryl group refers to an aryl group substituted with an alkyl group, and the preferred state of such alkyl and aryl groups is the same as that of the aforementioned alkyl and aryl groups. The alkenyl group with 3 to 20 carbon atoms is preferred, and the alkenyl group with 3 to 16 carbon atoms is even more preferred. Furthermore, these groups may also have known substituents within the scope of achieving the effects of the present invention.

[0222] R 01 and R 02 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, aralkyl or alkenyl groups, respectively.

[0223] The groups that decompose to produce a base-soluble group by the action of an acid, or that are removed by the action of an acid, are preferably trialkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are trialkyl ester groups or acetal groups.

[0224] Specifically, the following structures can be cited as examples of compounds having an alkoxymethyl group. Regarding compounds having an acetoxymethyl group, compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group can be cited. Various compounds can be cited as examples of compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule, but the list is not limited to these.

[0225] [Chemical Formula 28]

[0226] [Chemical Formula 29]

[0227] For compounds containing at least one of alkoxymethyl and aceoxymethyl, commercially available ones or those synthesized by known methods may be used. From the perspective of heat resistance, compounds in which alkoxymethyl or acetomethyl groups are directly substituted on the aromatic ring or trihalomethane ring are preferred.

[0228] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0229] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc. Urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea; Ethylene urea, including monohydroxymethylated ethoxyurea, dihydroxymethylated ethoxyurea, monomethoxymethylated ethoxyurea, dimethoxymethylated ethoxyurea, monoethoxymethylated ethoxyurea, diethoxymethylated ethoxyurea, monopropoxymethylated ethoxyurea, dipropoxymethylated ethoxyurea, monobutoxymethylated ethoxyurea, and dibutoxymethylated ethoxyurea, are crosslinking agents. Monohydroxymethylated fenprourea, dihydroxymethylated fenprourea, monomethoxymethylated fenprourea, dimethoxymethylated fenprourea, monoethoxymethylated fenprourea, diethoxymethylated fenprourea, monopropoxymethylated fenprourea, dipropoxymethylated fenprourea, monobutoxymethylated fenprourea, or dibutoxymethylated fenprourea are all fenprourea-based crosslinking agents; 1,3-Di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0230] Specific examples of benzoguanidine-based crosslinking agents include monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0231] In addition, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethyl phenyl ester, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenyl Methyl ketone, methoxymethylbenzoic acid methoxymethylphenyl ester, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0232] Other commercially available crosslinking agents can also be used. Among preferred commercially available agents are 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0233] Furthermore, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, cyclobutane compounds and benzo[a]oxane compounds as other crosslinking agents.

[0234] -Epoxy compounds (compounds containing epoxy groups)- As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not produce dehydration reactions caused by cross-linking, thus minimizing film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition of the present invention.

[0235] The presence of polyethylene oxide in the epoxy compound is preferred. This further reduces the elastic modulus and suppresses warpage. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, with 2 to 15 repeating units being preferred.

[0236] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkyl glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and silicones with epoxy groups such as polymethyl(glycidyloxypropyl)siloxane, but are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (these are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, and Rika... Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, manufactured by Daicel). (Manufactured by Nippon Kayaku Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds can also be used more preferably.

[0237]

Chemical Formula 30

[0238] In the formula, n is an integer from 1 to 5 and m is an integer from 1 to 20.

[0239] Among the above structures, considering both heat resistance and elongation, n = 1~2 and m = 3~7 are preferred.

[0240] -Oxycyclic butane compounds (compounds containing oxycyclic butane groups)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxybutane, 1,4-bis{[(3-ethyl-3-oxocyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxocyclobutane)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. is preferred, and two or more of these can be used alone or in combination.

[0241] -Benzoxazole compounds (compounds containing the benzoxazole group)- Because the cross-linking reaction is caused by the ring-opening addition reaction, the benzo[a]oxa compound does not produce degassing during hardening, thereby further reducing thermal shrinkage and inhibiting warping, which is therefore preferred.

[0242] Preferred examples of benzo[a]oxa compounds include Pd-type benzo[a]oxa, Fa-type benzo[a]oxa, (the above are product names, manufactured by Shikoku Chemicals Corporation), benzo[a]oxa adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a]oxa compounds. These can be used alone or in combination of two or more.

[0243] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may be two or more types. In the case of two or more other crosslinking agents, it is preferable that their total content is within the above-mentioned range.

[0244] <Alkali-generating agents> The resin composition of the present invention may include an alkali generating agent. The alkali generating agent is a compound capable of generating alkali through physical or chemical action. Preferred alkali generating agents for the resin composition of the present invention include thermal alkali generating agents and photo-alkali generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali-generating agent. By including a thermal alkali-generating agent in the resin composition, such as one that can promote the cyclization reaction of the precursor by heating, the mechanical properties or chemical resistance of the cured material are improved, for example, its performance as an interlayer insulating film for redistribution layers included in semiconductor packages becomes better. As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from a base-generating agent include secondary and tertiary amines. There are no particular limitations on the alkali-generating agent of the present invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonic acid acetamide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, and acetoimine compounds. Specific compounds that can be cited as nonionic base generating agents include those represented by formulas (B1), (B2), or (B3).

Chemical Formula 31

[0245] In formulas (B1) and (B2), Rb1, Rb2, and Rb3 are independently an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Rb1 and Rb2 do not simultaneously constitute hydrogen atoms. Furthermore, Rb1, Rb2, and Rb3 do not possess a carboxyl group. Moreover, in this specification, a tertiary amine structure refers to a structure where all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to the case where the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0246] In formulas (B1) and (B2), it is preferable that at least one of Rb1, Rb2, and Rb3 contains a cyclic structure, and it is even more preferable that at least two of them contain a cyclic structure. The cyclic structure can be any of a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. It is preferable that the monocyclic ring is a 5-membered or 6-membered ring, with a 6-membered ring being more preferred. It is preferable that the monocyclic ring is a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0247] More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), alkenyl groups (preferably with 2-24 carbon atoms, more preferably with 2-18 carbon atoms, and further preferably with 3-12 carbon atoms), aryl groups (preferably with 6-22 carbon atoms, more preferably with 6-18 carbon atoms, and further preferably with 6-10 carbon atoms), or aralkyl groups (preferably with 7-25 carbon atoms, more preferably with 7-19 carbon atoms, and further preferably with 7-12 carbon atoms). These groups may have substituents within the range that enables the effects of the present invention. Rb1 and Rb2 may be bonded to each other to form a ring. A nitrogen-containing heterocycle with 4-7 members is preferred as the formed ring. In particular, Rb 1 and Rb 2 are preferably straight-chain, branched or cyclic alkyl groups (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons) that may have substituents, and are preferably cycloalkyl groups (preferably with 3 to 24 carbons, more preferably with 3 to 18 carbons, and even more preferably with 3 to 12 carbons) that may have substituents, and are even more preferably cyclohexyl groups that may have substituents.

[0248] Examples of Rb 3 include alkyl groups (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), aryl groups (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-10 carbons), alkenyl groups (preferably with 2-24 carbons, more preferably with 2-12 carbons, and further preferably with 2-6 carbons), and aralkyl groups (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). The preferred groups are aryl (preferably 8-24 carbons, more preferably 8-20, and further preferably 8-16 carbons), alkoxy (preferably 1-24 carbons, more preferably 2-18, and further preferably 3-12 carbons), aryloxy (preferably 6-22 carbons, more preferably 6-18, and further preferably 6-12 carbons), or arylalkoxy (preferably 7-23 carbons, more preferably 7-19, and further preferably 7-12 carbons). Cycloalkyl (preferably 3-24 carbons, more preferably 3-18, and further preferably 3-12 carbons), aryl, and arylalkoxy groups. Rb3 may also have substituents within the scope of the effects of this invention.

[0249] The compound represented by formula (B1) is preferably the compound represented by formula (B1-1) or formula (B1-2) below.

Chemical Formula 32

[0250] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 have the same meaning as Rb 1 and Rb 2 in formula (B1). Rb 13 is an alkyl group (preferably with 1-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), an alkenyl group (preferably with 2-24 carbons, more preferably with 2-18 carbons, and further preferably with 3-12 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-12 carbons), or an aralkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons). Substituents may be present within the scope of the effects of this invention. Preferably, Rb 13 is an aralkyl group.

[0251] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbons, more preferably with 1 to 8 carbons, and even more preferably with 1 to 3 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 8 carbons, and even more preferably with 2 to 3 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), and a hydrogen atom is preferred.

[0252] Rb 35 is alkyl (preferably with 1-24 carbons, more preferably with 1-12 carbons, and even more preferably with 3-8 carbons), alkenyl (preferably with 2-12 carbons, more preferably with 2-10 carbons, and even more preferably with 3-8 carbons), aryl (preferably with 6-22 carbons, more preferably with 6-18 carbons, and even more preferably with 6-12 carbons), aralkyl (preferably with 7-23 carbons, more preferably with 7-19 carbons, and even more preferably with 7-12 carbons), with aryl being preferred.

[0253] Furthermore, the compound represented by formula (B1-1) is also preferred over the compound represented by formula (B1-1a).

Chemical Formula 33

[0254] Rb 11 and Rb 12 have the same meaning as Rb 11 and Rb 12 in equation (B1-1). Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 6 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 6 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), hydrogen atoms, or methyl groups are preferred. Rb 17 is an alkyl group (preferably with 1-24 carbons, more preferably with 1-12 carbons, and further preferably with 3-8 carbons), an alkenyl group (preferably with 2-12 carbons, more preferably with 2-10 carbons, and further preferably with 3-8 carbons), an aryl group (preferably with 6-22 carbons, more preferably with 6-18 carbons, and further preferably with 6-12 carbons), or an aralkyl group (preferably with 7-23 carbons, more preferably with 7-19 carbons, and further preferably with 7-12 carbons), wherein an aryl group is preferred.

[0255]

Chemical Formula 34

[0256] In formula (B3), L represents a hydrocarbon group, which is a hydrocarbon group with a divalent saturated hydrocarbon group in the path of the connecting chain linking adjacent oxygen and carbon atoms, and the number of atoms in the connecting chain path is three or more. Furthermore, RN1 and RN2 each independently represent a monovalent organic group.

[0257] In this specification, a "linking chain" refers to an atomic chain that connects two atoms or groups of atoms in the shortest possible (minimum number of atoms) path. For example, in the compound represented by the following formula, L is composed of phenyl-ethyl and has ethyl as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms in the path of the linking chain (that is, the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length") is 4.

Chemical Formula 35

[0258] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. An upper limit of 12 or less is more preferred, 10 or less is further preferred, and 8 or less is especially preferred. A lower limit of 4 or more is more preferred. From the viewpoint of rapidly carrying out the above-mentioned intramolecular cyclization reaction, an upper limit of 12 or less of the linking chain length of L is preferred, 8 or less is more preferred, 6 or less is further preferred, and 5 or less is especially preferred. In particular, a linking chain length of 4 or 5 is preferred, with 4 being optimal. Specific preferred compounds as base-generating agents include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0259] Furthermore, it is preferable that the alkali generating agent contains a compound represented by the following formula (N1).

Chemical Formula 36

[0260] In formula (N1), RN1 and RN2 independently represent monovalent organic groups, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0261] L is a divalent linker, and a divalent organic group is preferred. A linker chain length of 1 or more is preferred, and 2 or more is even better. As an upper limit, 12 or less is preferred, 8 or less is even better, and 5 or less is further preferred. The linker chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0262] In formula (N1), RN1 and RN2 independently represent monovalent organic groups (preferably with 1-24 carbon atoms, more preferably with 2-18, and further preferably with 3-12 carbon atoms) and hydrocarbon groups (preferably with 1-24 carbon atoms, more preferably with 1-12, and further preferably with 1-10 carbon atoms). Specifically, aliphatic hydrocarbon groups (preferably with 1-24 carbon atoms, more preferably with 1-12, and further preferably with 1-10) or aromatic hydrocarbon groups (preferably with 6-22 carbon atoms, more preferably with 6-18, and further preferably with 6-10 carbon atoms) are preferred. If aliphatic hydrocarbon groups are used as RN1 and RN2, the resulting base has high basicity, which is therefore preferred. Furthermore, aliphatic and aromatic hydrocarbon groups can have substituents, and the aliphatic and aromatic hydrocarbon groups can be in the aliphatic hydrocarbon chain or the aromatic ring, with oxygen atoms in the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0263] Examples of aliphatic hydrocarbon groups constituting RN1 and RN2 include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. Straight-chain or branched chain alkyl groups having 1 to 24 carbon atoms are preferred, 2 to 18 are more preferred, and 3 to 12 are even more preferred. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, dibutyl, tributyl, isopentyl, neopentyl, tripentyl, and isohexyl. Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even more preferred. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Groups relating to combinations of chain alkyl and cyclic alkyl groups are preferably composed of 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of groups relating to combinations of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. It is preferred that the alkyl group having oxygen atoms in the chain has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. From the viewpoint of increasing the boiling point of the alkali produced by decomposition (described later), it is preferable that RN1 and RN2 are alkyl groups with 5 to 12 carbon atoms. In formulations where close adhesion with metals (e.g., copper) is important, groups with cyclic alkyl groups or alkyl groups with 1 to 8 carbon atoms are preferred.

[0264] RN1 and RN2 can be interconnected to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, the ring structure formed by RN1 and RN2 can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the formed ring structure, a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1) is preferred. Examples include pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, piperidine rings, and morpholine rings. Pyrroleline rings, pyrrolidine rings, piperidine rings, piperidine rings, and morpholine rings are particularly preferred.

[0265] R C1 represents a hydrogen atom or a protecting group, with hydrogen atom being preferred.

[0266] As a protecting group, a protecting group that can be decomposed by the action of acid or base is preferred, and a protecting group that can be decomposed by acid can be given as an example.

[0267] Specific examples of protecting groups include chain-like or cyclic alkyl groups, or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tributyl, and cyclohexyl. Specifically, examples of chain-like alkyl groups having oxygen atoms in the chain include alkyloxyalkyl groups, and more specifically, examples include methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP).

[0268] There are no particular restrictions on the type of linker constituting the divalent L, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is even more preferred. The hydrocarbon group may have substituents and may also contain atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linker having an oxygen atom in the chain is preferred; groups relating to a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having an oxygen atom in the chain are even more preferred; a divalent aliphatic hydrocarbon group having an oxygen atom in the chain is further preferred. 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 (e.g., arylalkyl) related to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0269] As the linking group L, specifically, linear or branched chain alkyl groups, cyclic alkyl groups, groups relating to combinations of linear and cyclic alkyl groups, alkyl groups having oxygen atoms in the chain, linear or branched chain alkenyl groups, cyclic alkenyl groups, aryl groups, and aryl alkyl groups are preferred. It is preferred that the linear or branched alkyl groups have 1 to 12 carbon atoms, 2 to 6 carbon atoms are more preferred, and 2 to 4 carbon atoms are even more preferred. Cyclic alkyl groups with 3 to 12 carbon atoms are preferred, and those with 3 to 6 carbon atoms are even better. It is preferred that the groups associated with the combination of chain-like and cyclic-like alkyl groups have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkyl group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. It is preferred that the alkyl group containing oxygen atoms in the chain has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

[0270] The linear or branched chain-like alkenyl group having 2 to 12 carbon atoms is preferred, 2 to 6 is more preferred, and 2 to 3 is even more preferred. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferred to be 1 to 10, 1 to 6 is more preferred, and 1 to 3 is even more preferred. Cyclic alkenyl groups with 3 to 12 carbon atoms are preferred, and 3 to 6 carbon atoms are even more preferred. The number of C=C bonds in the cyclic alkenyl groups is preferably 1 to 6, even more preferred, and 1 to 2 carbon atoms are even more preferred. The aryl group with 6 to 22 carbon atoms is preferred, 6 to 18 is even better, and 6 to 10 is even more preferred. The arylalkyl group having 7 to 23 carbon atoms is preferred, 7 to 19 is even better, and 7 to 11 is further preferred. Among them, chain-like alkyl groups, cyclic alkyl groups, alkyl groups having oxygen atoms in the chain, chain-like alkenyl groups, aryl groups, aryl groups, and alkyl groups are preferred, and 1,2-ethylenyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylenyl (especially cis-vinylenyl), phenylenyl (1,2-phenylenyl), phenylmethylene (especially 1,2-phenylmethylene), and oxyethylenyl (especially 1,2-ethoxy-1,2-ethylenyl) are even more preferred.

[0271] Examples of alkali-generating agents can be given below, but the present invention is not limited thereto.

[0272]

Chemical Formula 37

[0273] The molecular weight of the nonionic hot alkali generator is preferably below 800, more preferably below 600, and further preferably below 500. As a lower limit, 100 or above is preferred, 200 or above is more preferred, and 300 or above is further preferred.

[0274] Preferred compounds for use as ionic base generators include, for example, those described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0275] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 38]

[0276] Specific examples of imine salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 39]

[0277] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of the resin in the resin composition of the present invention. A lower limit of 0.3 parts by weight or more is more preferred, and 0.5 parts by weight or more is further preferred. An upper limit of 30 parts by weight or less is more preferred, 20 parts by weight or less is further preferred, 10 parts by weight or less is even more preferred, and it can be 5 parts by weight or less, or 4 parts by weight or less. One or more alkali-generating agents can be used. When using two or more, it is preferable to keep the total dosage within the above-mentioned range.

[0278] <Metal adhesion modifier> The resin composition of the present invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonylurea structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0279] [Silane coupling agent] Examples of silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573, and these contents are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Also, it is preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0280]

Chemical Formula 40

[0281] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane. Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0282] [Aluminum-based adhesives] Examples of aluminum-based adhesives include aluminum tri(ethyl acetate)aluminum, tri(ethyl acetone)aluminum, and aluminum diisopropoxide of ethyl acetate.

[0283] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 may also be used, and such contents are incorporated into this specification.

[0284] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.1 to 30 parts by weight, more preferably in the range of 0.3 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion modifier, or there may be two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0285] <Migration Inhibitor> It is preferable that the resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0286] There are no particular limitations on the use of compounds as migration inhibitors, including those with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine 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, as well as tetraazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0287] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

[0288] Other migration inhibitors may be used, including the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073-0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, and these contents are incorporated into this specification.

[0289] The following compounds can be cited as specific examples of migration inhibitors. Among these, from the viewpoint of elongation at break and adhesion to the metal or resin layer, the migration inhibitors include tetrazolium, 5-aminotetrazole, and any one of the following M-4.

[0290]

Chemical Formula 41

[0291] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0292] Migration inhibitors can be one or more. When there are two or more migration inhibitors, it is preferable that their total number falls within the above-mentioned range. For example, from the viewpoint of elongation at break and adhesion to metal or resin layers, the use of tetrazolium and the aforementioned M-4 is preferred.

[0293] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0294] Specific compounds used as polymerization inhibitors include, preferably, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallnutol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2 -Nitrosino-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenthiazolinone, phenoxazolinone, 1,1-diphenyl-2-pyrrolidine, dibutyldithiocopper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Patent Application Publication No. 2015 / 125469 can also be used, and such contents are incorporated into this specification.

[0295] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0296] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that the total number is within the above range.

[0297] Acid scavenger To reduce performance changes caused by the passage of time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. The acid scavenger is a compound that can capture acid-producing compounds by being present in the system; compounds with low acidity and high pKa are preferred. As an acid scavenger, compounds having an amino group are preferred, including primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amides; primary amines, secondary amines, tertiary amines, and ammonium salts are preferred, with secondary amines, tertiary amines, and ammonium salts being even more preferred. Preferred acid scavengers include compounds having imidazole, diazabicyclic, ononium, trialkylamine, aniline, or pyridine structures; alkylamine derivatives having hydroxyl and / or ether bonds; and aniline derivatives having hydroxyl and / or ether bonds. In the case of an ononium structure, the acid scavenger is preferably a salt of a cation selected from ammonium, diazo, monium, strontium, phosphonium, pyridinium, etc., and an anion of an acid with a lower acidity than that produced by the acid generator.

[0298] Examples of acid scavengers with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclic structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having a onium structure include tetrabutylammonium hydroxide, triarylstromium hydroxide, benzylmethylstromium hydroxide, strom hydroxides having a 2-oxoalkyl group, specifically triphenylstromium hydroxide, tris(tert-butylphenyl)stromium hydroxide, bis(tert-butylphenyl)stromium hydroxide, benzylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid-scavenging agents having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0299] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecane), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyl... Dicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, succinyltriamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0300] These acid scavengers can be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger. However, when it contains an acid scavenger, the content of the acid scavenger is based on the total solid content of the composition, and is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

[0301] The preferred ratio of acid generator to acid scavenger is 2.5 to 300 (molar ratio). That is, from the viewpoint of sensitivity and resolution, a molar ratio of 2.5 or higher is preferred; from the viewpoint of suppressing the decrease in resolution caused by the thickening of the relief pattern over time from exposure to heat treatment, a ratio of 300 or lower is preferred. A molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0302] <Urea compounds, carbodiimide compounds, isourea compounds> From the viewpoint of elongation at break and adhesion to metal or resin layers, the resin composition of the present invention may contain at least one compound selected from the group consisting of urea compounds, carbodiimide compounds and isourea compounds (hereinafter also referred to as "urea compounds, etc."). Examples of urea compounds include those represented by formula (1-1), those represented by formula (1-2) and those represented by formula (1-3).

Chemical Formula 42

[0303] In formulas (1-1), (1-2), or (1-3), R11 and R12 independently represent aliphatic hydrocarbon groups with 1 to 7 carbon atoms that can have substituents, R21 and R22 independently represent aliphatic hydrocarbon groups with 1 to 7 carbon atoms that can have substituents, R31 and R32 independently represent aliphatic hydrocarbon groups with 1 to 7 carbon atoms that can have substituents, and R33 represents aliphatic hydrocarbon groups with 1 to 7 carbon atoms that can have substituents. In formula (1-1), R11 and R12 are respectively independently unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons or aliphatic hydrocarbon groups with 1 to 7 carbons having at least one substituent selected from the group including primary amine salt structure, secondary amine salt structure, tertiary amine group, tertiary amine salt structure and quaternary ammonium group as substituents, and are more preferably unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons. As for the unsubstituted aliphatic hydrocarbon group with 1 to 7 carbons in R 11 and R 12, it is preferred to be an unsubstituted saturated aliphatic hydrocarbon group with 1 to 7 carbons, and even more preferred to be an unsubstituted saturated aliphatic hydrocarbon group with 2 to 7 carbons, with ethyl, isopropyl, tributyl or cyclohexyl being more preferred.

[0304] In formula (1-1), R11 and R12 can each be an aliphatic hydrocarbon group with 2 to 7 carbon atoms having at least one substituent selected from the group consisting of hydroxyl, alkoxy, thiol and alkylthio groups. The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have more than 2 of the above-mentioned substituents, but the state having only 1 of the above-mentioned substituents is also one of the preferred states of the present invention.

[0305] In formula (1-2), R 21 and R 22 independently represent aliphatic hydrocarbon groups with 1 to 7 carbon atoms that can have substituents. In formula (1-2), it is preferable that R21 and R22 are unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons or aliphatic hydrocarbon groups with 1 to 7 carbons having amine or quaternary ammonium groups as substituents, and it is even more preferable that they are unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons. In formula (1-2), the preferred forms of the unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons in R 21 and R 22 or the aliphatic hydrocarbon groups with 1 to 7 carbons having the above-mentioned substituents are the same as those shown in the description of R 11 and R 12.

[0306] In formula (1-3), it is preferable that R 31 and R 32 are unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons or aliphatic hydrocarbon groups with 1 to 7 carbons having an amino group or a quaternary ammonium group as a substituent, and it is even more preferable that they are unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons. In formulas (1-3), the preferred forms of the unsubstituted aliphatic hydrocarbon groups with 1 to 7 carbons in R 31 and R 32 or the aliphatic hydrocarbon groups with 1 to 7 carbons having the above-mentioned substituents are the same as those shown in the descriptions of R 11 and R 12.

[0307] In formula (1-3), R 33 represents an aliphatic hydrocarbon group with 1 to 7 carbons that may have substituents. It is preferred to have an unsubstituted aliphatic hydrocarbon group with 1 to 7 carbons, and even more preferred to have an unsubstituted saturated aliphatic hydrocarbon group with 1 to 7 carbons, and even more preferred to have a saturated aliphatic hydrocarbon group with 1 to 4 carbons. In formula (1-3), methyl, ethyl, propyl, isopropyl, butyl or tributyl are preferred as R 33, and ethyl is even more preferred.

[0308] Specific examples of urea compounds include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited to these.

[0309] The total content of urea compounds, etc., relative to 100 parts by weight of a specific resin is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 8.0 parts by weight, and even more preferably 1.0 to 6.0 parts by weight. Urea compounds may be used alone or in combination with two or more. When two or more urea compounds are used simultaneously, it is preferable that their total content be within the range described above.

[0310] <Other Additives> The resin composition of the present invention can be combined with various additives as needed, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), within the scope of achieving the effects of the present invention. By appropriately containing these components, the physical properties of the membrane can be adjusted. Regarding these components, for example, reference can be made to paragraph 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812) and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and such contents are incorporated herein by reference. When these additives are used, it is preferable that their total amount is set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0311] [Surfactants] As surfactants, various surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. These surfactants can be nonionic, cationic, or anionic.

[0312] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially flowability) during preparation as a coating liquid are further improved, thereby further improving the uniformity of the coating thickness or the liquid-saving properties. That is, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the coated surface and the coating liquid is reduced, improving the wettability of the coated surface and thus improving the coating properties. Therefore, it is possible to form a film with a more uniform thickness and smaller thickness non-uniformity.

[0313] Examples of fluorinated surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO.,LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorinated surfactants may also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, and these contents are included in this specification. Block polymers can also be used as fluorinated surfactants. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and such contents are incorporated into this specification. Fluorinated surfactants can also preferably use fluorinated polymers, which contain repeating units from (meth)acrylate compounds having fluorine atoms and repeating units from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propyleneoxy groups). Examples of fluorinated surfactants used in this invention include the following compounds.

Chemical Formula 43

[0314] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorinated surfactants can also be used to treat fluoropolymers with vinyl unsaturated groups on their side chains. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available examples include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

[0315] Fluorinated surfactants are preferably composed of 3-40% by mass, more preferably 5-30% by mass, and especially preferably 7-25% by mass. Fluorinated surfactants within this fluorine content range are effective in terms of uniformity of coating thickness and liquid-saving properties, and also exhibit good solubility in the composition.

[0316] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0317] Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FAT CO.,LTD.).

[0318] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. As commercially available products, examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL&FAT CO.,LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

[0319] As cationic surfactants, examples include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymers Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co.,LTD.), and W001 (manufactured by Yusho Co.,Ltd.).

[0320] As anionic surfactants, examples include WO04, WO05, WO17 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0321] A single surfactant can be used, or two or more surfactants can be used in combination. The surfactant content relative to the total solids content of the composition is preferably 0.001~2.0% by mass, and even more preferably 0.005~1.0% by mass.

[0322] [Higher fatty acid derivatives] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide can be added to the resin composition of the present invention, so that they exist unevenly on the surface of the resin composition of the present invention during the drying process after coating.

[0323] Furthermore, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 may also be used for higher fatty acid derivatives, and such content is incorporated into this specification.

[0324] When the resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above-mentioned range.

[0325] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, thus further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiators also have the function of initiating polymerization through heat, and can sometimes be added as thermal polymerization initiators.

[0326] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as initiators of thermal free radical polymerization, and this content is incorporated into this specification.

[0327] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type or may contain two or more types. When two or more thermal polymerization initiators are included, the total amount within the above-mentioned range is preferred.

[0328] [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0329] The average particle size of the aforementioned inorganic particles is preferably 0.01~2.0 μm, more preferably 0.02~1.5 μm, further preferably 0.03~1.0 μm, and especially preferably 0.04~0.5 μm. The aforementioned average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be determined by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In cases where the above measurements are difficult to perform, measurements can also be performed using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0330] [Ultraviolet absorber] The composition of this invention may include a UV absorber. As a UV absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other UV absorbers can be used. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0331] Examples of acrylonitrile-based UV absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triphenyl terpenoid ultraviolet absorbers include mono(hydroxyphenyl)triphenyl compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl. 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triphenyl, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl, etc., are bis(hydroxyphenyl)triphenyl compounds; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triphenyl, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triphenyl, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triphenyl, etc., are tri(hydroxyphenyl)triphenyl compounds, etc.

[0332] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, it is preferable that the content of the ultraviolet absorber is 0.001% by mass or more and 1% by mass or less relative to the total solid content of the composition of the present invention, and even more preferably 0.01% by mass or more and 0.1% by mass or less.

[0333] [Organotitanium compounds] The resin composition of this embodiment may contain organotitanium compounds. Because the resin composition contains organotitanium compounds, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0334] As usable organotitanium compounds, examples include those in which the organic group is bonded to titanium atoms 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 with two or more alkoxy groups are preferred, as they exhibit excellent preservation stability of the resin composition and can achieve good curing patterns. Specific examples include diisopropanol bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropanol bis(2,4-pentanedione) titanium, diisopropanol bis(tetramethylheptanedione) titanium, and diisopropanol bis(ethyl acetate) titanium. II) Tetraalkoxy titanium compounds: such as tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenyl oxytitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc. III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenyl sulfonate) isopropoxide, etc. V) Titanium oxide compounds: such as titanium dioxide bis(pentanedione), titanium dioxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc. VI) Tetraacetone titanium compounds: such as tetraacetone titanium, etc. VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonate titanate, etc.

[0335] Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the group consisting of I) titanium chelates, II) tetraalkoxy titanium compounds and III) diacetic titanium compounds is preferred as an organotitanium compound. In particular, diisopropanol bis(acetyl ethyl acetate)titanium, tetra(n-butanol)titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

[0336] When an organotitanium compound is incorporated, the amount incorporated is preferably 0.05 to 10 parts by weight relative to 100 parts by weight of a specific resin, and more preferably 0.1 to 2 parts by weight. When the amount incorporated is 0.05 parts by weight or more, the resulting hardened pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when the amount incorporated is 10 parts by weight or less, the composition exhibits superior storage stability.

[0337] [Antioxidants] The composition of this invention may include an antioxidant. By including an antioxidant as an additive, the elongation properties of the hardened film and its adhesion to metallic materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. Compounds having a substituent at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both phenolic and phosphite groups within the same molecule are also preferred as antioxidants. Furthermore, phosphorus-based antioxidants can also be preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphine-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-heptacyclic-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, and this content is incorporated into this specification. Additionally, the composition of the present invention may contain potential antioxidants as needed. As potential antioxidants, compounds in which the site of antioxidant function is protected by a protecting group can be cited, and compounds in which the antioxidant function is achieved by heating at 100-250°C or heating at 80-200°C in the presence of an acid / base catalyst to remove the protecting group. As potential antioxidants, compounds described in International Patent Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 can be cited, and these contents are included in this specification. Commercially available products as potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0338]

Chemical Formula 44

[0339] In general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R6 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R7 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), or an organogroup containing at least one of an oxygen atom and a nitrogen atom in a 1 to 4 valence. k represents an integer from 1 to 4.

[0340] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metallic materials.

[0341] It can act on both resin and metal materials simultaneously, therefore, k being an integer from 2 to 4 is preferred. Examples of R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and it may also have substituents. Among these, from the viewpoint of solubility in the developer and metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion during the formation of metal complexes, -NH- is more preferred.

[0342] Regarding the compounds represented by general formula (3), the following can be cited as examples, but are not limited to the following structures.

[0343] [Chemical Formula 45]

[0344]

Chemical Formula 46

[0345] [Chemical Formula 47]

[0346] [Chemical Formula 48]

[0347] The amount of antioxidant added relative to the resin is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain the effect of improving elongation characteristics or adhesion to metal materials, even under high temperature and high humidity environments. Furthermore, by setting the amount added to 10 parts by weight or less, the sensitivity of the resin composition can be improved, for example, through interaction with photosensitizers. Only one type of antioxidant may be used, or two or more types may be used. When using two or more types, the total amount within the above-mentioned range is preferred.

[0348] [Anticoagulant] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0349] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination. The composition of the present invention may or may not contain an anti-coagulant, but when it does contain an anti-coagulant, it is preferable that the content of the anti-coagulant is 0.01% by mass or more and 10% by mass or less relative to the total solid content of the composition of the present invention, and more preferably 0.02% by mass or more and 5% by mass or less.

[0350] [Phenolic compounds] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION).

[0351] In this invention, a single phenolic compound may be used alone, or two or more may be used in combination. The composition of the present invention may contain phenolic compounds or may not contain phenolic compounds. However, when phenolic compounds are included, it is preferable that the content of phenolic compounds is 0.01% by mass or more and 30% by mass or less relative to the total solid content of the composition of the present invention, and more preferably 0.02% by mass or more and 20% by mass or less.

[0352] [Other polymers] Other examples of polymeric compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, phenolic varnish resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modifiers incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0353] In this invention, other polymer compounds can be used alone or in combination of two or more. The composition of the present invention may contain other polymeric compounds or may not contain other polymeric compounds. However, when other polymeric compounds are included, it is preferable that the content of other polymeric compounds is 0.01% by mass or more and 30% by mass or less relative to the total solid content of the composition of the present invention, and more preferably 0.02% by mass or more and 20% by mass or less.

[0354] <Properties of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm² / s to 12,000 mm² / s is preferred, 2,000 mm² / s to 10,000 mm² / s is more preferred, and 2,500 mm² / s to 8,000 mm² / s is even more preferred. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. When it is below 1,000 mm² / s, it is difficult to coat with the film thickness required for a reinsertion insulating film, for example, but when it is below 12,000 mm² / s, a coating film with excellent surface morphology can be obtained.

[0355] <Restrictions on substances contained in resin compositions> It is preferable that the moisture content of the resin composition of the present invention is less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. As long as it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining moisture content include adjusting the humidity of storage conditions and reducing the porosity of the storage container.

[0356] From an insulation point of view, it is preferable that the metal content of the resin composition of the present invention is less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above-mentioned range.

[0357] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention using a filter; and lining the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

[0358] Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion resistance, it is preferable that the halogen atom content is less than 500 ppm by mass, more preferably less than 300 ppm by mass, and further preferably less than 200 ppm by mass. Of these, it is preferable that the content of halogen ions is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or the total amount of chloride ions and bromide ions, is within the above-mentioned ranges. Ion exchange treatment is a good example of a method to regulate the content of halogen atoms.

[0359] As a container for the resin composition of the present invention, previously known containers can be used. Furthermore, as a container, in order to suppress the mixing of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle with an inner wall composed of six layers of six different resins, or a bottle in which the six resins are formed into a seven-layer structure. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0360] <Curing of resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The hardened product of the present invention is a hardened product obtained by hardening the resin composition of the present invention. Curing of the resin composition is preferably carried out by heating, with a heating temperature in the range of 120°C to 400°C being more preferred, in the range of 140°C to 380°C being further preferred, and in the range of 170°C to 350°C being particularly preferred. The morphology of the cured resin composition is not particularly limited, and it can be in the form of a film, rod, sphere, or granules, depending on the application. In this invention, the cured composition is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured composition can be selected according to applications such as forming a protective film on the wall surface, forming beer halls for conductivity, adjusting impedance or capacitance or internal stress, or imparting heat dissipation. The film thickness of the cured composition (the film formed by the cured composition) is preferably 0.5 μm or more and 150 μm or less. The cured composition can be used arbitrarily for both thin film and thick film applications. When using a thin film layer, 1 to 15 μm is preferred, 2 to 12 μm is more preferred, and 3 to 10 μm is further preferred. When using thick film layers, 15~50μm is preferred, 15~40μm is even better, and 15~30μm is even better. It is preferable that the shrinkage rate during curing of the resin composition of the present invention is 50% or less, more preferably 45% or less, and even more preferably 40% or less. Herein, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (Volume after hardening ÷ Volume before hardening) × 100

[0361] <Properties of cured resin compositions> The amide reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. As long as it is 70% or more, it will sometimes result in a cured product with excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0362] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out using previously known methods. Mixing can be achieved through methods such as mixing based on stirring blades, mixing based on ball mills, or mixing by rotating the tank itself. The optimal temperature for mixing is 10~30℃, and even better is 15~25℃.

[0363] Furthermore, to remove foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferable. Regarding the filter pore size, examples include 5 μm or less, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is preferred. The filter can be pre-cleaned with an organic solvent. In the filtration step, multiple filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be combined. For example, a configuration can be achieved by connecting a 1 μm pore size HDPE filter as the first stage and a 0.2 μm pore size HDPE filter as the second stage in series. Furthermore, various materials can be filtered multiple times. In the case of multiple filtrations, cyclic filtration can be performed. Filtration can also be performed after pressurization. When pressurizing and filtering, the pressurization pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using filters, impurity removal can also be performed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon. Furthermore, after filtration using a filter, a step can be performed where the resin composition filled in the bottle is placed under reduced pressure and degassed. [Example]

[0364] The present invention will be described in more detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise stated, "parts" and "%" are based on mass.

[0365] <Synthetic Example 1: Synthesis of Polymer P-1> 155.1 g of 4,4'-oxophthalic dianhydride (ODPA), 134.0 g of 2-hydroxyethyl methacrylate (HEMA), and 400 ml of γ-butyrolactone were added to a 2-liter separable flask. 79.1 g of pyridine was added while stirring at room temperature to obtain the reaction mixture. After the reaction was completed due to exothermic reaction, it was cooled to room temperature and allowed to stand for 16 hours. Next, under ice-cooled conditions, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Then, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and the mixture was stirred for 1 hour. Finally, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, yielding the reaction solution. The obtained reaction solution was added to 3 liters of ethanol, thereby generating a precipitate of crude polymer. The crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran, thereby obtaining a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the precipitate was filtered off and then vacuum dried to obtain powdered polymer P-1. The weight-average molecular weight (Mw) of polymer P-1 was determined to be 20,000.

[0366] <Synthesis Example 2: Synthesis of Polymer P-2> In Synthesis Example 1, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride was used instead of 155.1 g of 4,4'-oxophthalic acid dianhydride. Otherwise, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer P-2. The weight-average molecular weight (Mw) of polymer P-2 was determined to be 22,000.

[0367] <Synthetic Example 3: Synthesis of Polymer P-3> A diester of 4,4'-oxophthalic anhydride (obtained by drying 4,4'-oxophthalic acid at 140 °C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 18 hours to produce a diester of 4,4'-oxophthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 °C, and 16.12 g (135.5 mmol) of SOCl₂ was added over 10 minutes while maintaining the temperature at -10 ± 4 °C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at 20–23 °C. The reaction mixture was then stirred overnight at room temperature. Next, 5 L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, added to 4 L of water, stirred again for 30 minutes, and filtered off again. The obtained polyimide precursor was then dried at 45 °C for 3 days under reduced pressure to obtain polymer P-3. The weight-average molecular weight (Mw) of polymer P-3 was determined to be 18,000.

[0368] <Synthetic Example 4: Synthesis of Polymer P-4> In Synthesis Example 1, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) was not used. Otherwise, polymer P-4 was obtained by the same synthesis method as in Synthesis Example 1.

[0369] <Synthetic Example 5: Synthesis of Polymer P-5> In Synthesis Example 1, a mixture of 73.5 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and 77.5 g of 4,4'-oxophthalic acid dianhydride was used instead of 155.1 g of 4,4'-oxophthalic acid dianhydride. Otherwise, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer P-5. The weight-average molecular weight (Mw) of polymer P-5 was determined to be 22,000.

[0370] <Synthetic Example 6: Synthesis of Polymer P-6> In Synthesis Example 1, a mixture of 54.5 g of pyromellitic dianhydride and 77.5 g of 4,4'-oxophthalic dianhydride was used instead of 155.1 g of 4,4'-oxophthalic dianhydride. Otherwise, the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer P-6. The weight-average molecular weight (Mw) of polymer P-6 was determined to be 22,000.

[0371] <Synthesis Example 7: Synthesis of Polymer P-7> In Synthesis Example 1, 148.8 g of 2,2'-bis(trifluoromethyl)benzidine was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE), and the reaction was carried out in the same manner as described in Synthesis Example 1 to obtain polymer P-7. The weight-average molecular weight (Mw) of polymer P-7 was determined to be 20,000.

[0372] <Examples and Comparative Examples> In each embodiment, the components listed in the table below were mixed to obtain each photosensitive resin composition. Furthermore, in the comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of the components listed in the table is set to the amount recorded in the "parts by mass" section of the table. Furthermore, the solvent content in each component is set to the concentration of the solid component of the component as recorded in the table. The obtained photosensitive resin composition and the comparative composition were pressure filtered through a polytetrafluoroethylene filter with a pore size of 0.8 μm. Furthermore, in the table, a "-" indicates that the corresponding component is not present.

[0373]

Table 1

[0374]

Table 2

[0375]

Table 3

[0376]

Table 4

[0377] Table 5. Examples Example Example Example Example Comparative example Comparative example 33 34 35 36 37 1 2 resin type P-1 P-1 P-1 P-1 P-1 P-1 P-4 Quality 100 50 100 100 100 50 90 type - P-2 - - - P-2 - Quality - 50 - - - 50 - free radicals Crosslinking agent type M-1 M-1 M-1 M-1 M-1 M-1 M-2 Quality 8.5 8.5 8.5 8.5 8.5 8.5 8.5 Photopolymerization Initiator type I-2 I-1 I-3 I-3 I-3 I-1 I-2 Quality 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Hot alkali Producing agent type - - - - - - - Quality - - - - - - - polymerization Inhibitors type B-2 B-1 B-2 B-2 B-2 B-2 - Quality 0.05 0.06 0.05 0.05 0.05 0.05 - silane Coupling agent type C-1 C-2 C-2 C-2 C-1 C-2 - Quality 1.0 0.5 0.5 0.5 1.0 0.5 - type - C-3 C-3 C-3 - C-3 - Quality - 0.5 0.5 0.5 - 0.5 - migrate Inhibitors type D-1 - - - - - - Quality 0.3 - - - - - - type - - - - - - - Quality - - - - - - - additive type - J-1 J-1 - - J-1 J-2 Quality - 4 4 - - 4 3 type - - - - - - - Quality - - - - - - - type - - - - - - - Quality - - - - - - - solvent type NMP NMP NMP NMP NMP NMP GBL ratio 80 80 80 80 80 80 80 type EL EL EL EL EL EL DMSO ratio 20 20 20 20 20 20 20 Solid component concentration 42 42 42 42 42 42 42 Developer solvent type Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Quality 100 100 100 100 100 100 100 alkali type - - - - - - - Quality - - - - - - - Supply methods spray spray spray spray spray spray spray step Film thickness (μm) 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 Hardening temperature (°C) 180 240 180 180 180 180 180 Hardening time (min) 120 120 120 120 120 120 120 Rinse solution solvent type PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA Quality 99 99 95 95 95 100 100 type - - - - - - - Quality - - - - - - - alkali type Diisopropylethylamine Dimethylcyclohexylamine / diethanolamine Diisopropylethylamine Diisopropylethylamine Diisopropylethylamine - - Quality 1 0.5 / 0.5 5 5 5 - - Supply methods spray spray spray spray spray spray spray evaluate Elongation at break 80 75 80 80 81 40 38 Stacked reliability A A A A A D D

[0378] Table 6. Examples Example Example Example Example Example Example 38 39 40 41 42 43 44 resin type P-1 P-1 P-1 P-1 P-1 P-1 P-1 Quality 100 100 100 100 100 100 100 type - - - - - - - Quality - - - - - - - free radicals Crosslinking agent type M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 8.5 8.5 8.5 8.5 8.5 8.5 8.5 Photopolymerization Initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Hot alkali Producing agent type - - - - - - - Quality - - - - - - - polymerization Inhibitors type B-2 B-2 B-2 B-2 B-2 B-2 B-2 Quality 0.05 0.05 0.05 0.05 0.05 0.05 0.05 silane Coupling agent type C-2 C-2 C-2 C-2 C-2 C-2 C-2 Quality 0.5 0.5 0.5 0.5 0.5 0.5 0.5 type C-3 C-3 C-3 C-3 C-3 C-3 C-3 Quality 0.5 0.5 0.5 0.5 0.5 0.5 0.5 migrate Inhibitors type - - - - - - - Quality - - - - - - - type - - - - - - - Quality - - - - - - - additive type J-1 J-1 J-1 J-1 J-1 J-1 J-1 Quality 4 4 4 4 4 4 4 type - - - - - - - Quality - - - - - - - type - - - - - - - Quality - - - - - - - solvent type NMP NMP NMP NMP NMP NMP NMP ratio 80 80 80 80 80 80 80 type EL EL EL EL EL EL EL ratio 20 20 20 20 20 20 20 Solid component concentration 42 42 42 42 42 42 42 Developer solvent type Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Quality 100 100 100 100 100 100 100 alkali type - - - - - - - Quality - - - - - - - Supply methods Inverted Immersion Inverted Immersion spray Inverted Immersion Inverted Immersion Rotary Immersion / Spraying Inverted Immersion step Film thickness (μm) 20 8 8 20 8 20 20 PB temperature (°C) 100 100 100 100 100 100 100 Hardening temperature (°C) 180 180 180 180 180 180 180 Hardening time (min) 120 120 120 120 120 120 120 Rinse solution solvent type PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA PGMEA Quality 95 95 95 100 100 95 95 type - - - - - - - Quality - - - - - - - alkali type Diisopropylethylamine Diisopropylethylamine Diisopropylethylamine - - Diisopropylethylamine Diisopropylethylamine Quality 5 5 5 - - 5 5 Supply methods Inverted Immersion Inverted Immersion Inverted Immersion Inverted Immersion Inverted Immersion Inverted Immersion Rotary Immersion / Spraying evaluate Elongation at break 81 83 81 79 80 80 80 Stacked reliability A A A B A A A Alkaline treatment solution solvent type - - - Cyclopentanone Cyclopentanone - - Quality - - - 95 95 - - alkali type - - - Cyclohexyldimethylamine Cyclohexyldimethylamine - - Quality - - - 5 5 - - Supply methods - - - Inverted Immersion Inverted Immersion - -

[0379]

Table 7

[0380]

Table 8

[0381]

Table 9

[0382]

Table 10

Claims

1. A method for manufacturing a hardened material, comprising: The film forming step involves applying a photosensitive resin composition comprising a polyimide precursor having repeating units represented by the following formula (2) and a photopolymerization initiator onto a substrate to form a film; the exposure step involves selectively exposing the aforementioned film; the development step involves developing the aforementioned exposed film with a developing solution to form a pattern; the treatment step involves contacting the aforementioned pattern with an alkaline treatment solution comprising at least one compound selected from the group including alkali and alkali generating agents; and the heating step involves heating the pattern after the aforementioned treatment step, wherein the water content is 50% by mass or less relative to the total mass of the aforementioned alkaline treatment solution, the aforementioned alkaline treatment solution comprises propylene glycol monomethyl ether acetate, and the heating temperature in the aforementioned heating step is 120 to 230°C; [Chemical Formula 1] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R113 and R114 independently represent monovalent organic groups, R115 represents tetravalent organic groups, and R111 represents divalent organic groups.

2. The method for manufacturing a hardened material as described in claim 1, wherein the aforementioned alkaline treatment solution is a rinsing solution, and the aforementioned treatment step is a rinsing step of cleaning the aforementioned pattern with the aforementioned rinsing solution.

3. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned alkaline treatment solution contains an organic base as the aforementioned base.

4. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned alkaline treatment solution contains a secondary or tertiary amine as the aforementioned alkali.

5. A method for manufacturing a hardened material as claimed in claim 1 or claim 2, wherein the aforementioned heating step is a step of promoting the amide formation of the aforementioned polyamide precursor within the aforementioned pattern by heating using the action of at least one compound selected from the group consisting of the aforementioned alkali and alkali generated from the aforementioned alkali generating agent.

6. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned developing step is a step of supplying or continuously supplying the aforementioned developing solution to the aforementioned exposed film by spraying.

7. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the aforementioned processing step is a step of supplying or continuously supplying the aforementioned alkaline treatment solution to the aforementioned developed pattern by spraying.

8. A method for manufacturing a hardened material as described in claim 1 or claim 2, wherein the development in the aforementioned development step is negative development.

9. A method for manufacturing a laminate, which is a method for manufacturing a hardened material by repeating any one of claims 1 to 8.

10. The method for manufacturing a laminate as claimed in claim 9, further comprising a metal layer forming step of forming a metal layer on the hardened material during the aforementioned plurality of processes of manufacturing a hardened material.

11. A method for manufacturing a semiconductor device, comprising a method for manufacturing a cured material as described in any one of claims 1 to 8, or a method for manufacturing a multilayer as described in claim 9 or 10.

Images