Method for producing cured product, method for producing laminate, and method for producing semiconductor device

Abstract

The present invention provides: a method for producing a cured product, said method enabling the achievement of a cured product that exhibits excellent elongation at break and excellent chemical resistance even if cured at a low temperature; a method for producing a multilayer body, said method comprising the above-described method for producing a cured product; and a method for producing a semiconductor device, said method comprising the above-described method for producing a cured product or the above-described method for producing a multilayer body.　This method for producing a cured product comprises: a film formation step wherein a film is formed by applying a specific photosensitive resin composition onto a base material; a light exposure step wherein the film is selectively exposed to light; a development step wherein a pattern is formed by developing the film after the light exposure by means of a developer liquid; a treatment step wherein a treatment liquid and the pattern are brought into contact with each other; and a heating step wherein the pattern after the treatment step is heated. At least one of the developer liquid and the treatment liquid contains at least one compound that is selected from the group consisting of bases and base generators.

Description

[Technical field]

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

[0002] Resins such as polyimide are used in various applications due to their excellent heat resistance and insulating properties. Examples of such applications include, but are not limited to, the use of patterns containing these resins as insulating film or sealing material materials or protective films in the case of semiconductor devices for mounting. Patterns containing these resins are also used as base films or coverlays for flexible substrates.

[0003] For example, in the applications mentioned above, the cyclized resin, such as a polyimide, is used in the form of a photosensitive resin composition that includes a precursor of the cyclized resin, such as a polyimide precursor. Such a photosensitive resin composition is applied to a substrate by, for example, coating, and then, if necessary, exposed to light, developed, heated, or the like, whereby a cured product containing a cyclized resin (for example, a resin in which a polyimide precursor is imidized) can be formed on the substrate. The photosensitive resin composition can be applied by a known coating method, and can form fine patterns, patterns of complex shapes, and the like by development, and therefore has a high degree of freedom in designing the cured product, and can be said to have excellent adaptability in manufacturing. From the viewpoint of such excellent adaptability in manufacturing, in addition to the high performance of polyimides, etc., there are increasing expectations for the industrial application and development of a method for manufacturing a cured product using a photosensitive resin composition containing a polyimide precursor.

[0004] For example, Patent Document 1 describes a pattern formation method in which a photosensitive polyimide layer on a substrate is exposed to light to photocure it into an appropriate pattern, and then development is performed to remove the unexposed portions with a developer. The substrate on which the photocure polyimide pattern layer has been formed is then immersed in a rinsing solution for forming a photocure polyimide pattern layer, the rinsing solution containing at least 5 to 30% by volume of a primary aliphatic amino compound and 2 to 20% by volume of an aprotic basic solvent, to rinse the substrate, and finally, the substrate with the photocure polyimide layer removed from the rinsing solution is subjected to a heat treatment at high temperature. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 1-221741 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventionally, a photosensitive resin composition containing a precursor of a cyclized resin such as a polyimide precursor is applied to a substrate to form a film, the film is exposed to light, developed, and then heated to convert the precursor into a cyclized resin, producing a cured product. The cyclization improves the mechanical properties (e.g., elongation at break) of the film, improving the reliability of the module. In the production of the above-mentioned cured product, it is desired to provide a method for producing the cured product that can give a cured product having excellent breaking elongation and chemical resistance even when cured at a low temperature. Specifically, for example, the cured product is used as an interlayer insulating film for a rewiring layer. Here, the substrates on which the insulating films are used are becoming larger in area, from 8-inch wafer size to 12-inch and even panel-level size. Also, the number of layers to be stacked in order to install wiring such as copper wiring is gradually increasing from 1 layer to 2 layers, 3 layers, 4 layers, and 5 layers. As the area of ​​the substrate increases and the number of polyimide layers increases during such manufacturing, warping of the wafer or panel becomes more noticeable, and it is therefore desirable to perform the above-mentioned heating at a low temperature (for example, 230° C. or lower). However, when the above-mentioned heating is performed at a low temperature, the cyclized resinification (cyclization) does not proceed sufficiently, and the breaking elongation of the film may decrease.

[0007] Up to now, attempts have been made to introduce a base into a photosensitive resin composition in order to ensure that cyclization (eg, imidization) proceeds sufficiently even when heating is performed at a low temperature. When a base is directly added to a photosensitive resin composition, cyclization in the precursor of the cyclized resin may proceed even during storage of the photosensitive resin composition, resulting in a significant change in the viscosity of the composition. When a photobase generator, which is a base precursor, is added, a base, which is an inhibitor of the acid and radicals, is generated simultaneously with the acid and radicals that promote the formation of a negative image in the exposed area during exposure, which may cause the problem of reducing sensitivity. In addition, it is difficult to add a large amount of the base generator to the composition in terms of formulation, and the effect of promoting cyclization during heating is limited. In order to improve the chemical resistance of the cured product, it is possible to use a polyfunctional polymerizable compound having three or more functional groups as the polymerizable compound contained in the composition. However, when a polyfunctional polymerizable compound having three or more functional groups is used, crosslinking of the polymerizable compound proceeds during heating together with or prior to the cyclization, and the crosslinked structure makes it difficult for the cyclization to proceed in the film, which may result in poor breaking elongation.

[0008] The present invention aims to provide a method for producing a cured product that can give a cured product that has excellent breaking elongation and chemical resistance even when cured at low temperature, a method for producing a laminate that includes the method for producing the cured product, and a method for producing a semiconductor device that includes the method for producing the cured product or the method for producing the laminate. [Means for solving the problem]

[0009] Examples of typical embodiments of the present invention are given below. <1> a film-forming step of applying a photosensitive resin composition containing a precursor of a cyclized resin, a photopolymerization initiator, and a trifunctional or higher polymerizable compound onto a substrate to form a film; an exposure step of selectively exposing the film to light; a developing step of developing the exposed film with a developer to form a pattern; a treatment step of contacting the pattern with a treatment liquid; and a heating step of heating the pattern after the treatment step, At least one of the developer and the processing liquid contains at least one compound selected from the group consisting of bases and base generators. A method for producing a cured product. <2> The processing liquid is a rinse liquid. <1> A method for producing the cured product according to claim 1. <3> the processing step is a rinsing step of cleaning the pattern with the processing liquid; <1> or <2> A method for producing the cured product according to claim 1. <4> The developer contains an organic solvent in an amount of 50% by mass or more based on the total mass of the developer. <1> ~ <3> 13. A method for producing the cured product according to any one of the above items. <5> The treatment liquid contains at least one compound selected from the group consisting of a base and a base generator. <1> ~ <4> 13. A method for producing the cured product according to any one of the above items. <6> The base comprises an organic base. <1> ~ <5> 13. A method for producing the cured product according to any one of the above items. <7> The base comprises a secondary amine or a tertiary amine. <1> ~ <6> 13. A method for producing the cured product according to any one of the above items. <8> The precursor of the cyclized resin is a polyimide precursor containing a repeating unit represented by the following formula (2): <1> ~ <7> 13. A method for producing the cured product according to any one of the above items. [ka] In formula (2), A 1 and A 2 each independently represents an oxygen atom or -NH-; R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R113 and R 114 each independently represents a hydrogen atom or a monovalent organic group. <9> the heating step is a step of promoting cyclization of the precursor of the cyclized resin in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator through heating. <1> ~ <8> 13. A method for producing the cured product according to any one of the above items. <10> The heating temperature in the heating step is 120 to 230°C. <1> ~ <9> 13. A method for producing the cured product according to any one of the above items. <11> The developing step is a step of supplying the developer to the exposed film by showering or a step of continuously supplying the developer to the exposed film. <1> ~ <10> 13. A method for producing the cured product according to any one of the above items. <12> The development in the developing step is a negative development. <1> ~ <11> 13. A method for producing the cured product according to any one of the above items. <13> <1> ~ <12> 13. A method for producing a laminate, comprising repeating the method for producing a cured product according to any one of the above items a plurality of times. <14> The method further includes a metal layer forming step of forming a metal layer on the cured product during the multiple steps of the method for producing the cured product. <13> A method for producing the laminate described in claim 1. <15> <1> ~ <12> A method for producing a cured product according to any one of the above, or <13> Or <14> A method for manufacturing a semiconductor device, comprising the method for manufacturing a stack according to claim 1. Effect of the Invention

[0010] According to the present invention, there are provided a method for producing a cured product that can give a cured product having excellent breaking elongation and chemical resistance even when cured at a low temperature, a method for producing a laminate that includes the method for producing the cured product, and a method for producing a semiconductor device that includes the method for producing the cured product or the method for producing the laminate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect. In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formulae represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) unless otherwise specified, and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using 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 as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction. In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH. As used herein, combinations of preferred aspects are more preferred aspects.

[0012] (Method of producing the cured product) The method for producing a cured product of the present invention includes a film formation step of applying a photosensitive resin composition containing a cyclized resin precursor, a photopolymerization initiator, and a trifunctional or higher polymerizable compound onto a substrate to form a film, an exposure step of selectively exposing the film to light, a development step of developing the exposed film with a developer to form a pattern, a treatment step of contacting a treatment liquid with the pattern, and a heating step of heating the pattern after the treatment step, wherein at least one of the developer and the treatment liquid contains at least one compound selected from the group consisting of bases and base generators.

[0013] According to the method for producing a cured product of the present invention, even when cured at low temperatures, a cured product having excellent breaking elongation and chemical resistance can be obtained. The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

[0014] In the method for producing a cured product of the present invention, it is believed that at least one of the developer and the processing liquid contains at least one compound selected from the group consisting of a base and a base generator, so that the base or the base generator penetrates into the image area. As a result, in the subsequent heating step, cyclization such as imidization proceeds quickly due to the action of the base or the base generated from the base generator, and it is presumed that crosslinks of the polyfunctional polymerizable compound having three or more functional groups are also formed after cyclization such as imidization has progressed sufficiently. From the above, it is presumed that both breaking elongation and chemical resistance can be achieved.

[0015] Here, Patent Document 1 does not disclose the use of a photosensitive resin composition containing a precursor of a cyclized resin (hereinafter, the precursor of the cyclized resin is also referred to as a "specific resin"), a photopolymerization initiator, and a polymerizable compound having three or more functionalities, and that at least one of the developer and the treatment liquid contains at least one compound selected from the group consisting of a base and a base generator. The method for producing the cured product of the present invention will now be described in detail.

[0016] <Film formation process> The method for producing a cured product of the present invention includes a film-forming step of applying a photosensitive resin composition (hereinafter also simply referred to as a "resin composition") onto a substrate to form a film. The photosensitive resin composition used in the present invention will be described in detail later.

[0017] [Base material] The type of substrate can be appropriately determined depending on the application, and includes, but is not limited to, substrates for semiconductor preparation such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs). In the present invention, substrates for semiconductor preparation are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred. Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface. The shape of the substrate is not particularly limited, and may be circular or rectangular. The size of the substrate is, for example, a diameter of 100 to 450 mm, preferably 200 to 450 mm, if it is circular, and, for example, a length of a short side of 100 to 1000 mm, preferably 200 to 700 mm, if it is rectangular. As the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

[0018] Furthermore, when a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0019] The resin composition of the present invention is preferably applied to a substrate by coating.

[0020] Specific examples of the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, more preferred are spin coating, slit coating, spray coating, and inkjet methods, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration and coating conditions of the resin composition according to the method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and for circular substrates such as wafers, spin coating, spray coating, inkjet, etc. are preferred, while for rectangular substrates, slit coating, spray coating, inkjet, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate. Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention. Also, a process may be performed to remove excess film from the edge of the substrate, such as edge bead rinse (EBR) or back rinse. Furthermore, a pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate, thereby improving the wettability of the substrate, and then the resin composition is applied.

[0021] <Drying process> After the film-forming step (layer-forming step), the above-mentioned film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. Drying may be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0022] <Exposure process> The film is subjected to an exposure step to selectively expose the film to light. That is, the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film. The amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention. For example, the amount of exposure light is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 is preferable, and 200 to 8,000 mJ / cm 2 is more preferred.

[0023] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0024] In terms of the light source, the exposure wavelength may be, for example, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet (EUV) (wavelength 13.6nm), (6) electron beam, (7) YAG laser second harmonic 532nm, third harmonic 355nm, etc. For the resin composition of the present invention, exposure by a high pressure mercury lamp is particularly preferred, and among these, exposure by i-line is preferred. This makes it possible to obtain a particularly high exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.

[0025] <Post-exposure baking process> The film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step. The post-exposure baking step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably from 1 to 12° C. / min, more preferably from 2 to 10° C. / min, and even more preferably from 3 to 10° C. / min, from the temperature at the start of heating to the maximum heating temperature. The rate of temperature rise may be appropriately changed during heating. The heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0026] <Developing process> After exposure, the film is subjected to a development step in which it is developed with a developer to form a pattern. That is, the method for producing a cured product of the present invention includes a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern. Here, development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development. In the present invention, the development in the development step is preferably negative development.

[0027] [Developer] In the present invention, a developer is a liquid used to form an image by removing unexposed or exposed areas. The developer used in the development step includes a developer containing an organic solvent.

[0028] The developer may be an ester, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyl alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, 2-methoxy ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., as well as ethers and Examples of such ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide. Furthermore, when the developer contains a base as described below, and the base (for example, an organic base) as described below is liquid in the environment in which the developer is used, the base as described below can be used as both a solvent and a base.

[0029] The solvent of the developer may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

[0030] The content of the solvent in the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the developer. The content may be 100% by mass.

[0031] -Bases, base generators- The developer may contain at least one compound selected from the group consisting of bases and base generators. In the present invention, at least one of the developer and the processing solution contains at least one compound selected from the group consisting of bases and base generators. Among them, it is preferable that the treatment liquid contains at least one compound selected from the group consisting of a base and a base generator. In addition, in order to suppress swelling of the pattern due to the base during development, the developer does not contain either a base or a base generator, and the treatment liquid contains at least one compound selected from the group consisting of a base and a base generator, which is also one of the preferred embodiments of the present invention. According to the above embodiment, the variation in the pattern shape may be suppressed. Examples of preferred compounds as the base and base generator include preferred compounds as the base and base generator contained in the treatment liquid described below.

[0032] The developer may further comprise other components. Examples of other components include known surfactants and known defoamers.

[0033] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. For thin films, from the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred. For thick films, from the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, paddle development, in which the developer supplied through a nozzle is kept stationary, is more preferred. The above-mentioned developing methods (e.g., a combination of paddle development and shower development, or a combination of paddle development and straight development) may be used in combination. For example, paddle development has the effect of swelling the film to facilitate penetration of the subsequent processing liquid, while shower development and spray development have the effect of improving the removability of non-image areas. Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times. As a method of supplying the developer in the development process, a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a combination of these processes can be used. Among these, the developing step is preferably a step in which the developer is supplied to the exposed film by a method of widely spraying the developer, such as spraying or showering, or is supplied continuously.

[0034] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0035] <Processing steps> The method for producing a cured product of the present invention includes a treatment step of contacting the above-mentioned pattern with a treatment liquid. The processing step is preferably a rinsing step of cleaning the pattern with the processing liquid. The processing liquid is preferably a rinse liquid. That is, the treatment step is preferably a rinsing step in which the pattern (the pattern obtained in the developing step) is washed with a rinsing liquid.

[0036] [Processing solution] The treatment liquid is a liquid that comes into contact with the pattern after development, and is, for example, a liquid used to remove residues after development and to clean the pattern. The treatment liquid may also be a liquid used for purposes other than removing residues after development and cleaning the pattern, such as a liquid used to come into contact with the pattern after cleaning. In the method for producing a cured product of the present invention, the treatment step may be carried out multiple times. When the treatment step is carried out multiple times, all of the treatment steps may be carried out using a treatment liquid containing at least one compound selected from the group consisting of a base and a base generator (hereinafter also referred to as a "base-containing treatment liquid"), or the treatment steps may be carried out in combination, for example, by carrying out a treatment step using a treatment liquid containing neither a base nor a base generator and a treatment step using a base-containing treatment liquid once each. When the treatment step is carried out multiple times, the following embodiments (1) to (4) can be mentioned, for example. (1) An embodiment in which a rinsing step is performed in which a pattern is cleaned using a treatment liquid (rinsing liquid) that does not contain a base, and then a rinsing step is performed in which a pattern is cleaned using a treatment liquid (rinsing liquid) that contains a base. (2) An embodiment in which a rinsing step of cleaning a pattern using a base-containing treatment liquid (rinsing liquid) is performed multiple times. (3) An embodiment including a step of contacting a pattern with a base-containing treatment liquid after a rinsing step of cleaning the pattern with a treatment liquid (rinsing liquid) that does not contain a base. (4) An embodiment including a step of contacting a pattern with a base-containing treatment liquid (rinsing liquid) after a rinsing step of cleaning the pattern with the base-containing treatment liquid (rinsing liquid) is performed. In the above (3) and (4), the step of contacting the pattern with the base-containing treatment liquid does not necessarily have to be intended for cleaning the pattern. When the treatment steps are carried out a plurality of times, it is preferable to carry out all the treatment steps before the heating step described below. The treatment liquid used in the method for producing a cured product of the present invention preferably has a water content of 50 mass % or less based on the total mass of the treatment liquid. The water content is more preferably 20% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 2% by mass or less. The lower limit of the water content is not particularly limited, and may be 0 mass %.

[0037] As the processing liquid, for example, a solvent that is different from the solvent contained in the developer (for example, an organic solvent different from the organic solvent contained in the developer) and that contains at least one compound selected from the group consisting of bases and base generators can be used.

[0038] -base- As the base, from the viewpoint of reliability when the base remains in the cured film (adhesion to the substrate when the cured product is further heated), an organic base is preferable. The base is preferably a base having an amino group, and preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, or the like. In order to promote the imidization reaction, a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferable, a secondary amine, a tertiary amine, or an ammonium salt is more preferable, a secondary amine or a tertiary amine is even more preferable, and a tertiary amine is particularly preferable. From the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferable for the base to be one that is unlikely to remain in the cured film (obtained cured product), and from the viewpoint of promoting imidization, it is preferable for the base to be one that is unlikely to decrease in the amount remaining before heating due to evaporation, etc. Therefore, the boiling point of the base is preferably from 30°C to 350°C, more preferably from 80°C to 270°C, and further preferably from 100°C to 230°C at normal pressure (101,325 Pa). Furthermore, the boiling point of the base is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the treatment liquid, and more preferably higher than the boiling point of the organic solvent contained in the treatment liquid. For example, when the boiling point of the organic solvent is 100°C, the base used preferably has a boiling point of 80°C or higher, and more preferably has a boiling point of 100°C or higher.

[0039] Specific examples of the base contained in the treatment solution include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diazabicyclo[2.2.2]octane, and the like. aminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine. Among these, from the viewpoints of breaking elongation and chemical resistance, it is preferable that the treatment liquid contains, as a base, dimethylcyclohexylamine, dimethylpiperidine, butanediamine, tetramethylammonium hydroxide, N,N-diisopropylethylamine, triethylamine, diethanolamine, N,N-dimethylaniline, or aniline.

[0040] When a base is contained, the content of the base relative to the total mass of the treatment liquid is preferably from 0.05 to 50 mass %, more preferably from 0.05 to 20 mass %, and further preferably from 0.1 to 10 mass %. The base may be used alone or in combination of two or more. When two or more bases are used in combination in the treatment liquid, the total content thereof is preferably within the above-mentioned range.

[0041] -Base generator- The treatment liquid may contain a base generator. The base generator may be a photobase generator or a thermal base generator, with a thermal base generator being preferred. As the photobase generator or thermal base generator, for example, the photobase generators or thermal base generators explained below as components contained in the photosensitive resin composition can be used without any particular limitation.

[0042] When a base generator is contained, the content of the base generator relative to the total mass of the treatment liquid is preferably from 0.005 to 50 mass %, more preferably from 0.05 to 20 mass %, and further preferably from 0.1 to 10 mass %. The base generator may be used alone or in combination of two or more. When two or more base generators are used in combination in the treatment liquid, the total content thereof is preferably within the above-mentioned range.

[0043] Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-methyl-2-propanediol, ... -Alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-alkyloxypropionate, etc.) ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers. Examples of the dimethyl ether include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide. Furthermore, when the above-mentioned base (for example, an organic base) is liquid in the environment in which the treatment liquid is used, the above-mentioned base can be used as both a solvent and a base.

[0044] When the treatment liquid contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, cyclohexane, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, cyclohexanone, cyclohexane, PGMEA, and PGME are more preferred, and cyclohexanone, cyclohexane, and PGMEA are even more preferred.

[0045] When the treatment liquid contains an organic solvent, the treatment liquid preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. In addition, the treatment liquid may contain 100% by mass of the organic solvent.

[0046] The treatment liquid may further contain other components. Examples of other components include known surfactants and known defoamers.

[0047] [Method of Supplying Processing Solution] The method of supplying the treatment liquid is not particularly limited as long as the treatment liquid can be brought into contact with the pattern obtained in the development step, and for example, a mode of supplying the treatment liquid onto the pattern obtained in the development step can be mentioned. The supply method is not particularly limited, and includes a method of immersing the substrate in the treatment liquid, supplying the treatment liquid onto the substrate by a paddle (liquid puddle), supplying the treatment liquid onto the substrate by a shower, and continuously supplying the treatment liquid onto the substrate by a means such as a straight nozzle. From the viewpoints of the permeability of the treatment liquid into the image area, the removability of the non-image areas, and production efficiency, there are methods of supplying the treatment liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the treatment liquid using a nozzle is preferred. From the viewpoint of the permeability of the treatment liquid into the image area, a method in which the treatment liquid supplied using a nozzle is maintained on the substrate is more preferred. The above-mentioned methods for supplying the base-containing treatment solution (for example, a combination of supply by paddle and supply by shower, or supply by paddle and supply by straight nozzle) may be used in combination. For example, paddle supply has the effect of swelling the film to facilitate penetration of the subsequent processing solution, while shower supply or spray supply has the effect of improving the removability of non-image areas. In addition, it is sufficient that a base-containing processing solution is used in at least one of the combined methods. Here, in the present invention, a treatment step using a base-containing treatment liquid may be performed after a treatment liquid not containing a base and a base generator is supplied onto a pattern (for example, after a treatment liquid not containing a base and a base generator is supplied onto a pattern and the pattern is washed). In the above embodiment, the method for supplying the treatment liquid containing neither a base nor a base generator onto the pattern is not particularly limited, but may be supplying the treatment liquid by a paddle. In the above embodiment, the method for supplying the base-containing treatment liquid onto the pattern is not particularly limited, but preferred examples include supply by shower, supply by straight nozzle, and the like. It is considered that by supplying a base-free processing solution by a paddle, the pattern swells, and at least one compound selected from the group consisting of a base and a base generator in the base-containing processing solution to be supplied later is more likely to penetrate into the pattern, and the effect of improving the breaking elongation, etc. is more likely to be obtained. In addition, by supplying the base-containing processing solution by a shower, a straight nozzle, etc., the removal property (rinsing property) of development residue, etc. may be excellent in some cases. As a method of supplying the treatment liquid in the treatment process, a process in which the treatment liquid is continuously supplied to the substrate, a process in which the treatment liquid is kept substantially stationary on the substrate, a process in which the treatment liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these processes can be used. Among these, the treating step is preferably a step in which the treating solution is supplied to the developed pattern by a method of widely spraying the treating solution, such as spraying or showering, or is supplied continuously. It is also preferred that the development in the development step is carried out by paddle development, and at least one of the supplies of the base-containing treatment solution in the treatment step is carried out by shower supply or continuous supply by a straight nozzle, etc. According to the above embodiment, it is considered that the pattern is swollen by paddle development, so that at least one compound selected from the group consisting of a base and a base generator in the base-containing treatment solution is easily permeated into the pattern, and effects such as improved breaking elongation are more easily obtained.

[0048] The treatment time in the treatment step (i.e., the time during which the treatment liquid is in contact with the pattern) is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the treatment liquid during the treatment step is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0049] <Heating process> The pattern obtained by the development step (pattern after the treatment step) is subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention includes a heating step of heating the pattern obtained in the developing step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the polymerizable compound other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450° C., more preferably 130 to 250° C., and even more preferably 150 to 230° C. In order to suppress warping of the wafer or panel, it is preferable to heat at a low temperature, and in this case, the heating temperature (maximum heating temperature) is preferably 150 to 200° C., more preferably 150 to 190° C., and even more preferably 150 to 180° C.

[0050] The heating step is preferably a step of promoting cyclization of the precursor of the cyclized resin in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator (i.e., a base contained in at least one of the developer and the processing liquid or a base generated from the base generator) through heating, and more preferably a step of promoting imidization of the polyimide precursor in the pattern.

[0051] The heating step is preferably performed at a temperature rise rate of 1 to 12° C. / min from the starting temperature to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min. By setting the temperature rise rate at 1° C. / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate at 12° C. / min or less, it is possible to alleviate the residual stress of the cured product. Additionally, in the case of an oven capable of rapid heating, the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C. / sec, more preferably 2 to 7° C. / sec, and even more preferably 3 to 6° C. / sec.

[0052] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after drying, and is preferably raised from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0053] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and further preferably from 15 to 240 minutes.

[0054] In particular, when forming a multi-layer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, further preferably 240° C. or less, particularly preferably 230° C. or less, and can be 200° C. or less.

[0055] Heating may be performed stepwise. For example, the following steps may be performed: increasing the temperature from 25°C to 120°C at 3°C / min, holding at 120°C for 60 minutes, increasing the temperature from 120°C to 180°C at 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to perform the treatment while irradiating with ultraviolet light as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film characteristics. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, a first pretreatment step may be performed in the range of 100 to 150°C, and then a second pretreatment step may be performed in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C. / min.

[0056] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0057] <Post-development exposure process> The pattern obtained by the development step (pattern after the treatment step) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step to light. The pattern obtained by the development step (pattern after the treatment step) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step to light. In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted. In the post-development exposure step, it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm, calculated as the exposure energy at the wavelength to which the photosensitive compound has sensitivity. 2 and preferably 100 to 15,000 mJ / cm 2 It is more preferable that: The post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0058] <Metal layer formation process> The pattern obtained by the development step (preferably subjected to the heating step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably subjected to a heating step).

[0059] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferable, and copper is even more preferable.

[0060] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, JP-A-2004-101850, U.S. Patent No. 7,888,181B2, and U.S. Patent No. 9,177,926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods can be considered. More specifically, sputtering, a patterning method that combines photolithography and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned. A preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.

[0061] The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm, at the thickest portion.

[0062] <Application> The method for producing the cured product of the present invention or the fields in which the cured product of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc. In addition, examples include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), and pattern formation by etching of insulating films for mounting applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd., "High-performance and Applied Technology of Polyimides," April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, "Basics and Development of Polyimide Materials," published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association, "Latest Polyimides: Basics and Applications," NTS, August 2010.

[0063] The method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0064] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate of the present invention is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers. Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0065] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a laminate of the present invention multiple times.

[0066] The laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times. A preferred embodiment of the metal layer forming step is as described above. As the laminate, for example, a laminate having at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. The layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0067] <Lamination process> The method for producing the laminate of the present invention preferably includes a lamination step. The lamination process is a series of processes including (a) a film forming process (layer forming process), (b) an exposure process, (c) a development process, (d) a treatment process, (e) and a heating process, which are carried out again on the surface of the pattern (resin layer) or metal layer, in this order. However, the film forming process (a) and the heating process (d) may be repeated. In addition, the heating process (e) may be followed by a metal layer forming process (f). It goes without saying that the lamination process may further include the drying process and the like as appropriate.

[0068] In the case where a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0069] The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times. For example, a structure of 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred. The layers may be the same or different in composition, shape, film thickness, etc.

[0070] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, (d) treatment step, (e) heating step, and (f) metal layer formation step, or the steps may be repeated in the order of (a) film formation step, (d) heating step, and (f) metal layer formation step. The resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step.

[0071] (Surface activation treatment process) The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually carried out after the metal layer forming step, but after the above-mentioned development step, the resin composition layer may be subjected to a surface activation treatment step before the metal layer forming step. The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer on which the resin composition layer is formed. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved. In addition, it is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved. Specifically, the surface activation treatment is selected from plasma treatment with various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, etching treatment with CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, surface treatment by ultraviolet (UV) ozone method, immersion in an aqueous hydrochloric acid solution to remove the oxide film, followed by immersion in an organic surface treatment agent containing a compound having at least one amino group and one thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the source gas is particularly preferred. In the case of corona discharge treatment, the energy is 500 to 200,000 J / m 2 is preferable, and 1000 to 100,000 J / m 2 More preferably, 10,000 to 50,000 J / m 2 is most preferred.

[0072] (Method of manufacturing semiconductor devices) The present invention also discloses a method for producing a semiconductor device, including the method for producing the cured product of the present invention or the method for producing the laminate of the present invention. Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP2016-027357A, the contents of which are incorporated herein by reference.

[0073] (Photosensitive resin composition) The photosensitive resin composition is a photosensitive resin composition used in the method for producing a cured product of the present invention, the method for producing a laminate of the present invention, or the method for producing a semiconductor device of the present invention. The photosensitive resin composition of the present invention contains a precursor of a cyclized resin, a photopolymerization initiator, and a tri- or higher functional polymerizable compound. Hereinafter, each component contained in the photosensitive resin composition (also simply referred to as a resin composition) of the present invention will be described in detail.

[0074] <Specific resin> The resin composition of the present invention contains a precursor of a cyclized resin (specific resin). The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bonding chain in a resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide. The precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin. A resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred. Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. That is, the resin composition of the present invention preferably contains, as the specific resin, at least one type of resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. In addition, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described below, and more preferably contains a radical polymerization initiator described below and also contains a radical polymerizable compound described below. If necessary, the resin composition of the present invention may further contain a sensitizer described below. For example, a negative photosensitive film is formed from such a resin composition of the present invention. The specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. For example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed from the resin composition of the present invention.

[0075] [Polyimide precursor] The polyimide precursor used in the present invention is not particularly limited in terms of its type, but it preferably contains a repeating unit represented by the following formula (2). [ka] In formula (2), A 1 and A 2 each independently represents an oxygen atom or -NH-; R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0076] A in Equation (2) 1 and A 2 each independently represents an oxygen atom or -NH-, and an oxygen atom is preferable. R in Equation (2) 111represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, a group represented by -Ar- and -Ar-L-Ar- is exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. Here, each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

[0077] R 111 is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it is preferable that the diamine contains a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and it is more preferable that the diamine contains an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

[0078] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from these combinations, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-, and still more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0079] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-Diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether , 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine , bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl can be mentioned.

[0080] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0081] In addition, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598 are also preferably used.

[0082] R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the obtained organic film. However, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group. It is more preferable that Ar is a phenylene group, and L is -O-.

[0083] Also, R 111From the viewpoint of i-line transmittance, it is preferable that the divalent organic group represented by the following formula (51) or formula (61) is used. In particular, from the viewpoints of i-line transmittance and ease of availability, it is more preferable that the divalent organic group represented by the formula (61) is used. Formula (51) [ka] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group; R 50 ~R 57 At least one of these is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 each independently represents a fluorine atom, a methyl group, or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

[0084] R in Equation (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [ka] In formula (5), R 112 R is a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, a group selected from -O-, -CO-, -S-, -SO2-, -NHCO-, and a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, a group selected from -O-, -CO-, -S-, and -SO2-, and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-. 112 is most preferably a single bond or -O-.

[0085] R 115 Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. 115 As a structure corresponding to the above, only one type of tetracarboxylic dianhydride residue may be contained, or two or more types may be contained. For example, from the viewpoint of breaking elongation and adhesion to a metal or resin layer, it is preferable to use a polyimide precursor having one molecule of R 115 As the above, the structure represented by formula (5) is represented by R 112 is a single bond, and R 112 Also preferred is an embodiment including a structure in which: The tetracarboxylic dianhydride is preferably represented by the following formula (O). [ka] In formula (O), R 115 R represents a tetravalent organic group. 115 The preferred range of R in formula (2) is 115 The same definition and preferred range are also the same.

[0086] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2 ',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-Benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0087] Further, preferred examples include the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598.

[0088] R in Equation (2) 113 and R 114Each of R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. 113 and R 114 It is preferable that at least one of R contains a polymerizable group, and it is more preferable that both of R contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the above groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group of the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0089] [ka]

[0090] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201Examples of the alkylene group include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CHCH(OH)CH-, and polyalkyleneoxy group, of which alkylene groups such as ethylene group and propylene group, -CHCH(OH)CH-, cyclohexyl group, and polyalkyleneoxy group are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy group are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

[0091] In formula (2), R 113 is a hydrogen atom, or R 114 When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0092] In formula (2), R 113 and R 114 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0093] It is also preferable that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0094] In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be used as the diamine.

[0095] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it is possible to further widen the width of the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, R 111 and R 112 each independently represents a divalent organic group; R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; R 113 and R 114At least one of the groups is a group containing a polymerizable group, and it is preferable that both of the groups are groups containing a polymerizable group.

[0096] A 1 , A 2 , R 111 , R 113 and R 114 Each independently represents A in formula (2). 1 , A 2 , R 111 , R 113 and R 114 The same definition and preferred range are also the same. R 112 is R in Eq. (5). 112 The same definition and preferred range are also the same.

[0097] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. In addition, it may contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0098] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be the repeating unit represented by formula (2).

[0099] 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 3,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 8,000 to 20,000. The polyimide precursor has a molecular weight dispersity of preferably 1.8 or more, more preferably 2.0 or more, and even more preferably 2.2 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight / number average molecular weight. In addition, when the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.

[0100] [Polybenzoxazole precursor] The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3). [ka] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.

[0101] In formula (3), R 123 and R 124 are R in Eq. (2), 113 In other words, it is preferable that at least one of them is a polymerizable group. In formula (3), R 121 R represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. 121The dicarboxylic acid residue is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types of dicarboxylic acid residues may be used.

[0102] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred. The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula.

[0103] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0104] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only a group having an aromatic group and two -COOH groups are more preferred.

[0105] [ka] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-, and each * independently represents a bonding site to another structure.

[0106] Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0107] In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group is R 115 The same definition and preferred range are also the same. R 122is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols may be used alone or in combination.

[0108] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0109] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, or -NHCO-, and * and # each represent a bonding site with another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. 122 It is also preferable that R is a structure represented by the above formula. 122is a structure represented by the above formula, any two of the four * and # are R 122 is a bonding site with the nitrogen atom to which it is bonded, and the other two are R 122 is preferably a bonding site with the oxygen atom to which the bond is bonded, and the two * are preferably R 122 is a bonding site with the oxygen atom to which it is bonded, and the two #'s are R 122 is a bonding site with the nitrogen atom to which it is bonded, or two * are R 122 is a bonding site with the nitrogen atom to which it is bonded, and the two #'s are R 122 is more preferably a bonding site with the oxygen atom to which the bond is bonded, and two * are 122 is a bonding site with the oxygen atom to which it is bonded, and the two #'s are R 122 It is more preferable that the nitrogen atom to which the group is bonded is the bonding site.

[0110] The bisaminophenol derivative is also preferably a compound represented by the formula (As). [ka]

[0111] In formula (As), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

[0112] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

[0113] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, i.e., at R3, is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, which is particularly preferred in that the effect of achieving a high cyclization rate when cured at low temperatures is further enhanced.

[0114] In addition, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, since this maintains the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

[0115] In the formula (As), R1 is more preferably alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene pertaining to R1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in that they can provide a well-balanced polybenzoxazole precursor having sufficient solubility in a solvent while maintaining the effects of high transparency to i-line and high cyclization rate when cured at low temperature.

[0116] For the production method of the bisaminophenol derivative represented by the above formula (As), reference can be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

[0117] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Of course, it goes without saying that the present invention is not limited to these.

[0118] The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of formula (3) above. The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that the occurrence of warping due to ring closure can be suppressed.

[0119] [ka] In formula (SL), Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, and R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and a+b is 100 mol %.

[0120] In formula (SL), preferred Z is R in the b structure. 5s and R 6s is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, and to simultaneously achieve the effect of suppressing warpage and the effect of improving solvent solubility.

[0121] When the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Examples of such a tetracarboxylic acid residue include R 115 Examples include:

[0122] The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. In addition, when the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as one resin are each within the above ranges.

[0123] [Polyamide-imide precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-; R 113 represents a hydrogen atom or a monovalent organic group.

[0124] In formula (PAI-2), R 117is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0125] Also, R 117is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two of the carboxy groups may be converted into acid anhydrides. The optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor includes branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0126] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0127] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or a phenylene group. These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0128] In formula (PAI-2), R 111 , A 2 , R113 are R in the above formula (2), 111 , A 2 , R 113 The same applies to the preferred embodiments.

[0129] The polyamideimide precursor may further comprise other repeat units. Examples of other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1). [ka]

[0130] In formula (PAI-1), R 116 represents a divalent organic group, R 111 represents a divalent organic group. In formula (PAI-1), R 116 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0131] Also, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound. The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0132] Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0133] Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and hexadecafluorosuccinic acid. Examples of the fluorosebacic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

[0134] In formula (PAI-1), R 111 is R in the above formula (2). 111 The same applies to the preferred embodiments.

[0135] It is also preferable that the polyamideimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0136] In order to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, the polyamide-imide precursor may be copolymerized with bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like, as the diamine component.

[0137] An embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all of the repeating units in the polyamideimide precursor except for the terminals may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminals may be either the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

[0138] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly specified, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the resin composition contains multiple types of polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide precursor are within the above range. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimide precursors as one resin are each within the above range.

[0139] [Method for producing polyimide precursor, etc.] The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, is more preferable. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like. In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0140] -End capping agent- In the method for producing a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve storage stability. When capping the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability. Preferred examples of monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of the amino groups include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents. In addition, when the amino group at the resin end is blocked, it can be blocked with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferably carboxylic acid anhydrides and carboxylic acid chlorides. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. Preferred examples of the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0141] -Solid precipitation- The production of polyimide precursors and the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain polyimide precursors and the like. In order to improve the degree of purification, the polyimide precursors and the like may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

[0142] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0143] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R 115 It is preferable that the polyimide precursor contains two or more different polyimide precursors. For example, from the viewpoint of breaking elongation and adhesion to a metal or resin layer, for example, R 115 is a structure represented by the above formula (5), 112 a polyimide precursor having a structure in which R is a single bond; 115 is a structure represented by the above formula (5), 112 and a polyimide precursor containing a structure in which:

[0144] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin"). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound having a high polymerizable group value and a weight average molecular weight of 50,000 or less (for example, a polymerizable compound having a molar content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin having a molecular weight of at least 100 mol / g to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0145] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition. In addition, the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition. In addition, as a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0146] [Photopolymerization initiator] The photosensitive resin composition contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.

[0147] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L mol -1 ·cm -1 It is preferable that the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) using ethyl acetate as a solvent.

[0148] Any known compound can be used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP Patent No. 6301489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018 / 221177 A, the photopolymerization initiators described in WO 2018 / 110179 A, ​​the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 A are mentioned, and the contents of these are also incorporated herein.

[0149] Examples of the ketone compound include the compounds described in paragraph 0087 of JP2015-087611A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0150] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in JP-A-4225898 can be used, the contents of which are incorporated herein by reference.

[0151] Examples of α-hydroxyketone initiators that can be used include 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 (product names: all manufactured by BASF).

[0152] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF).

[0153] As the aminoacetophenone-based initiator, compounds having a maximum absorption wavelength matching a light source having a wavelength of 365 nm or 405 nm, etc., as described in JP-A-2009-191179 can also be used, the contents of which are incorporated herein by reference.

[0154] Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

[0155] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0156] As the photoradical polymerization initiator, more preferably, an oxime compound is used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0157] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP-T-2004-534797 A, compounds described in JP-A-2017-019766 A, compounds described in Japanese Patent No. 6065596 A, compounds described in WO 2015 / 152153 A, compounds described in WO 2017 / 051680 A, compounds described in JP-A-2017-198865 A, compounds described in paragraphs 0025-0038 of WO 2017 / 164127 A, compounds described in WO 2013 / 167515 A, and the like, the contents of which are incorporated herein by reference.

[0158] Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photoradical polymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0159] [ka]

[0160] Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photoradical polymerization initiator 2 described in JP-A-2012-014052). In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831, and Adeka Arcles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. In addition, DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. In addition, an oxime compound having the following structure can also be used. [ka]

[0161] As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466 and JP-A-06636081, the contents of which are incorporated herein by reference.

[0162] As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0163] In addition, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, paragraph 0345, and compound (C-3) described in JP-A-2013-164471, paragraph 0101, the contents of which are incorporated herein by reference.

[0164] As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, the contents of which are incorporated herein. In addition, an example of the oxime compound having a nitro group is Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

[0165] As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can be used. Specific examples include OE-01 to OE-75 described in WO 2015 / 036910.

[0166] As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, the contents of which are incorporated herein by reference.

[0167] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1 Examples of the electron-withdrawing group of include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and even more preferably an alkoxy group, an alkylsulfanyl group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group.

[0168] The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [ka] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; R X3 ~R X14 each independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0169] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0170] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0171] Most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0172] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0173] More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

[0174] In addition, the photoradical polymerization initiator may be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketone such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) may be used.

[0175] [ka]

[0176] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R I01 is a group represented by formula (II), or R I00 is the same group as R I02 ~R I04 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0177] [ka]

[0178] In the formula, R I05 ~R I07 is R in the above formula (I). I02 ~R I04 is the same as:

[0179] In addition, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0180] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is reduced and the solubility in a solvent or the like is improved, so that precipitation is less likely to occur over time, and the stability over time of the resin composition can be improved. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015 / 004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; compounds (C) and (D) described in WO-2016 / 033680; Examples of the photoinitiator include Cmpd1 to 7 described in Japanese Patent Publication No. 34963, the oxime ester photoinitiator described in paragraph 0007 of JP-T-2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiator described in Japanese Patent Publication No. 6469669, the contents of which are incorporated herein by reference.

[0181] The content of the photopolymerization initiator is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, further preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0182] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate Examples of such an alkyl ether compound include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Among these, from the viewpoints of breaking elongation and adhesion to a metal or resin layer, a compound having an ethanolamine structure or a compound having a coumarin structure is preferred, and N-phenyldiethanolamine or (7-(diethylamino)coumarin-3-carboxylate) is more preferred. Other sensitizing dyes may also be used. For details about the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of JP2016-027357A, the contents of which are incorporated herein by reference.

[0183] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and further preferably 0.5 to 10 mass%, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more kinds.

[0184] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of the chain transfer agent include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to a low activity radical to generate a radical, or are oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

[0185] In addition, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of WO 2015 / 199219 can also be used, the contents of which are incorporated herein by reference.

[0186] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be one type or two or more types. When two or more types of chain transfer agents are used, the total is preferably within the above range.

[0187] <Polymerizable compound> The resin composition of the present invention contains a tri- or higher functional polymerizable compound. In the present invention, a tri- or higher functional polymerizable compound refers to a compound containing three or more polymerizable groups in the structure. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a radically polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloxy group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloxy group is more preferable. Specific examples of polymerizable groups other than the radical polymerizable group include an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Among these, as the trifunctional or higher functional polymerizable compound, a compound containing three or more radically polymerizable groups (hereinafter, also referred to as "trifunctional or higher functional radically polymerizable compound") is preferable.

[0188] [Radically polymerizable compounds with three or more functional groups] The trifunctional or higher functional radical polymerizable compound is a compound containing 3 or more radical polymerizable groups, and may be a compound containing 4 or more radical polymerizable groups, a compound containing 5 or more radical polymerizable groups, or a compound containing 6 or more radical polymerizable groups. For example, the trifunctional or higher functional radical polymerizable compound preferably contains 3 to 15 radical polymerizable groups, more preferably contains 3 to 10 radical polymerizable groups, and further preferably contains 3 to 6 radical polymerizable groups. The molecular weight of the trifunctional or higher radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 700 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 300 or more. The tri- or higher functional radically polymerizable compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional radical polymerizable compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid tri(meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0189] Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. Commercially available products of these include KAYARAD D-330, D-310, D-320, DPHA (all manufactured by Nippon Kayaku Co., Ltd.), A-TMMT, A-DPH (all manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. Modified compounds of these (e.g., ethylene oxide modified, propylene oxide modified, caprolactone modified, etc.) and oligomer type compounds of these can also be used.

[0190] Examples of the tri- or higher functional radically polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0191] The tri- or higher functional radical polymerizable compound also includes tri- or higher functional urethane (meth)acrylate. Examples of trifunctional or higher urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0192] When a radically polymerizable compound having three or more functionalities is contained, the content is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0193] The trifunctional or higher radical polymerizable compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

[0194] [Difunctional or less radical polymerizable compounds] It is also preferable that the resin composition of the present invention further contains a radically polymerizable compound having two or less functionalities (that is, a compound containing one or two radically polymerizable groups in the structure). In particular, when the resin composition of the present invention contains a radically polymerizable compound having three or more functionalities, an embodiment containing a radically polymerizable compound having three or more functionalities and a radically polymerizable compound having two or less functionalities is also one of the preferred embodiments of the present invention. As the difunctional or lower radical polymerizable compound, it is preferable to use a difunctional methacrylate or acrylate from the viewpoints of pattern resolution and film stretchability. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as necessary. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain. In the resin composition of the present invention, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), a monofunctional radical polymerizable compound can also be preferably used as the radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.

[0195] When a radically polymerizable compound having two or less functionalities is contained, the content is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less. In addition, the content of the radically polymerizable compounds having two or less functionalities relative to the total mass of the radically polymerizable compounds (the sum of the total mass of the radically polymerizable compounds having two or less functionalities and the total mass of the radically polymerizable compounds having three or more functionalities) is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. The lower limit is not particularly limited, and may be 0% by mass.

[0196] The radical polymerizable compound having two or less functionalities may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

[0197] [Other polymerizable compounds] The resin composition of the present invention also preferably contains another polymerizable compound different from the above-mentioned radically polymerizable compound. In the present invention, the other polymerizable compound refers to a polymerizable compound other than the above-mentioned radical polymerizable compound, and is preferably a compound having in its molecule a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having in its molecule a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof under the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0198] The resin composition of the present invention may contain another tri- or higher functional polymerizable compound instead of or in addition to the tri- or higher functional radical polymerizable compound. Furthermore, the resin composition of the present invention may contain other polymerizable compounds having two or less functionalities, in addition to other polymerizable compounds having three or more functionalities. Furthermore, the resin composition of the present invention may contain, in addition to the above-mentioned tri- or higher functional radical polymerizable compound, other di- or lower functional polymerizable compound. The other polymerizable compounds will be described below. In the following description, a compound having three or more polymerizable groups corresponds to another trifunctional or more polymerizable compound, and a compound having two or less polymerizable groups corresponds to another bifunctional or less polymerizable compound.

[0199] As the other polymerizable compound, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other polymerizable compounds include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and it is sufficient that the compound has the same structure as the compound produced by the above method.In addition, the methylol groups of these compounds may be self-condensed to produce an oligomer. As the above-mentioned amino group-containing compound, a polymerizable compound using melamine is called a melamine-based polymerizable compound, a polymerizable compound using glycoluril, urea or alkylene urea is called a urea-based polymerizable compound, a polymerizable compound using alkylene urea is called an alkylene urea-based polymerizable compound, and a polymerizable compound using benzoguanamine is called a benzoguanamine-based polymerizable compound. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based polymerizable compounds and melamine-based polymerizable compounds, and more preferably contains at least one compound selected from the group consisting of glycoluril-based polymerizable compounds and melamine-based polymerizable compounds described below.

[0200] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6. The molecular weight of the above compound is preferably 1,500 or less, and more preferably 180 to 1,200.

[0201] [ka]

[0202] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0203] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0204] [ka]

[0205] In the formula, X represents a single bond or a divalent organic group, and each R 104 each independently represents an alkyl group or an acyl group; R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which decomposes under the action of an acid to produce an alkali-soluble group (for example, a group which is eliminated under the action of an acid, -C(R 4 )2COOR 5 A group represented by R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 5 represents a group which is eliminated by the action of an acid. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. A group that decomposes under the action of an acid to produce an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37)(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Furthermore, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.

[0206] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0207] The group which decomposes under the action of an acid to generate an alkali-soluble group, or the group which is eliminated under the action of an acid, is preferably a tertiary alkyl group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0208] Specific examples of compounds having an alkoxymethyl group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds is changed to an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0209] [ka]

[0210] [ka]

[0211] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0212] Specific examples of the melamine-based polymerizable compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0213] Specific examples of the urea-based polymerizable compound include glycoluril-based polymerizable compounds such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based polymerizable compounds such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; ethyleneurea-based polymerizable compounds such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea; propylene urea-based polymerizable compounds such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, and dibutoxymethylated propylene urea; Examples include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0214] Specific examples of the benzoguanamine-based polymerizable compound include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0215] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0216] As the other polymerizable compounds, commercially available products may be used. Suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35X. L, 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.), Nikalac (registered trademark, the same applies below) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0217] The resin composition of the present invention also preferably contains, as another polymerizable compound, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0218] -Epoxy compounds (compounds having epoxy groups)- The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200°C or less, and does not undergo a dehydration reaction due to the crosslinking, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the resin composition of the present invention at low temperatures and suppressing warping.

[0219] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 2 to 15.

[0220] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) BEO-20E, Likaresin (registered trademark) BEO-60E, Likaresin (registered trademark) HBE-100, Likaresin (registered trademark) DME-100, Likaresin (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S , EP-3950S (all trade 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 (all trade names, manufactured by Daicel CORPORATION), 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 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. The following compounds are also preferably used.

[0221] [ka]

[0222] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0223] Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0224] -Oxetane compounds (compounds having an oxetanyl group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

[0225] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

[0226] Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0227] When the resin composition contains other trifunctional or higher functional polymerizable compounds, the content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, further preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass% based on the total solid content of the resin composition of the present invention. The other trifunctional or higher functional polymerizable compounds may contain only one type, or may contain two or more types. When the other trifunctional or higher functional polymerizable compounds contain two or more types, the total is preferably within the above range.

[0228] When the resin composition contains other polymerizable compounds having two or less functionalities, the content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, further preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass% based on the total solid content of the resin composition of the present invention. The other polymerizable compounds having two or less functionalities may be contained in only one type, or in two or more types. When two or more types of other polymerizable compounds having two or less functionalities are contained, the total is preferably within the above range.

[0229] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. The photoacid generator is preferably a photoacid generator that can generate an acid by being exposed to light, either alone or in combination with a sensitizer. Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0230] Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.

[0231] Examples of the quinone diazide compound include a monovalent or polyvalent hydroxy compound to which the sulfonic acid of quinone diazide is ester-bonded, a monovalent or polyvalent amino compound to which the sulfonic acid of quinone diazide is sulfonamide-bonded, and a polyhydroxy polyamino compound to which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds do not have to be substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By including such a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.

[0232] Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOCP. -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC HP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriM L-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP -PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product name, Asahi Yu Examples of suitable phenols include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resins.

[0233] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0234] Specific examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0235] Among these, it is preferable that the quinone diazide compound contains a phenol compound and an ester of 4-naphthoquinone diazide sulfonyl group, which can provide higher sensitivity to i-line exposure and higher resolution.

[0236] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, it is possible to obtain a contrast between the exposed and unexposed parts, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

[0237] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), or the below-described formula (OS-103), formula (OS-104), or formula (OS-105).

[0238] [ka]

[0239] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group, or a halogen atom. 3 When there are a plurality of X's, they may be the same or different. 3The alkyl group and alkoxy group in the above formula (X) may have a substituent. 3 The alkyl group in the above formula (X) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 The alkoxy group in the above formula (I) is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in is preferably a chlorine atom or a fluorine atom. In formula (OS-1), m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 may be the same or different. In formula (OS-1), R 34 represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may 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 halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0240] In formula (OS-1), m3 is 3, and X 3 is a methyl group, and X 3 The substitution position of is the ortho position, and R 34 Particularly preferred are compounds in which R is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group.

[0241] Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP2011-209692A and paragraphs 0158 to 0167 of JP2015-194674A, the contents of which are incorporated herein by reference.

[0242] [ka]

[0243] In formula (OS-103) ~ formula (OS-105), R s1 R represents an alkyl group, an aryl group, or a heteroaryl group, and may be present in plural. s2 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and may be present in plurality. s6 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 0 to 6. In formula (OS-103) ~ formula (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the following formula may have a known substituent as long as the effects of the present invention can be obtained.

[0244] In formula (OS-103) ~ formula (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. s2 Among R, it is preferable that one or two of them are an alkyl group, an aryl group, or a halogen atom, it is more preferable that one of them is an alkyl group, an aryl group, or a halogen atom, and it is particularly preferable that one of them is an alkyl group and the remaining one is a hydrogen atom. s2 The alkyl group or aryl group represented by the following formula (I) may have a known substituent as long as the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, and is preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

[0245] In formulae (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1; and when Xs is S, ns is preferably 2. In formula (OS-103) ~ formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the following formula may have a substituent. In formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0246] Furthermore, the compound represented by formula (OS-103) above is particularly preferably a compound represented by formula (OS-106), formula (OS-110) or formula (OS-111) below; the compound represented by formula (OS-104) above is particularly preferably a compound represented by formula (OS-107) below; and the compound represented by formula (OS-105) above is particularly preferably a compound represented by formula (OS-108) or formula (OS-109) below. [ka]

[0247] In formula (OS-106) ~ formula (OS-111), R t1 represents an alkyl group, an aryl group, or a heteroaryl group; R t7 represents a hydrogen atom or a bromine atom, 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; R t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; R t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0248] In formula (OS-106) ~ formula (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, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0249] In formula (OS-106) ~ formula (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom. R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the above oxime sulfonate compound, the stereochemical structure (E, Z) of the oxime may be either one or a mixture. Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP-A No. 2011-209692 and paragraphs 0168 to 0194 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference.

[0250] Other preferable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

[0251] [ka]

[0252] In formula (OS-101) or formula (OS-102), R u9R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. u9 is more preferably a cyano group or an aryl group, u9 More preferably, is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 each independently represents an alkyl group or an aryl group.

[0253] In formula (OS-101) or formula (OS-102), R u1 ~R u4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of the rings may be bonded to each other to form a ring. In this case, the rings may be condensed to form a condensed ring together with the benzene ring. u1 ~R u4 is preferably a hydrogen atom, a halogen atom or an alkyl group, and R u1 ~R u4 It is also preferable that at least two of R are bonded to each other to form an aryl group. u1 ~R u4 is preferably a hydrogen atom. Each of the above-mentioned substituents may further have a substituent.

[0254] The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195 to 0207 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred. [ka] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Chemical Industries, Ltd.).

[0255] Further, compounds represented by the following structural formulas are also preferred examples. [ka]

[0256] Specific examples of the organic halogenated compounds include those described in Wakabayashi et al., Bull Chem. Soc Japan, vol. 42, p. 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-4605 / 1971, JP-A-36281 / 1973, JP-A-32070 / 1980, JP-A-239736 / 1985, JP-A-169835 / 1986, JP-A-169837 / 1987, JP-A-58241 / 1987, JP-A-212401 / 1987, JP-A-70243 / 1988, JP-A-298339 / 1988, and M.P. Hutt, Journal of Heterocyclic Chemistry, vol. 1 (No. 3), (1970), the contents of which are incorporated herein by reference. In particular, preferred examples include oxazole compounds substituted with a trihalomethyl group: S-triazine compounds. More preferably, an s-triazine derivative having at least one mono-, di-, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, riazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples of the bis(trichloromethyl)-s-triazine include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0257] Examples of the organic borate compounds include those described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, JP-A-2002-116539, and Kunz, Martin, "Rad Tech '98. Proceedings of April organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561; organic boron iodine complexes described in JP-A-6-175554 and JP-A-6-175553; Specific examples include organoboron phosphonium complexes described in JP-A-9-188710, and organoboron transition metal coordination complexes described in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like, the contents of which are incorporated herein by reference.

[0258] Examples of the disulfone compounds include compounds described in JP-A-61-166544 and JP-A-2001-132318, and diazodisulfone compounds.

[0259] Examples of the onium salt compound include diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and TSBal et al., Polymer, 21, 423 (1980); ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049; phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056; iodine salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP-A-2-150848 and JP-A-2-296514. sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581; selenonium salts described in JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047(1979); arsonium salts described in C.S.Wen et al., Teh., Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct. (1988); and onium salts such as pyridinium salts, the contents of which are incorporated herein by reference.

[0260] The onium salt includes onium salts represented by the following general formulas (RI-I) to (RI-III). [ka] In formula (RI-I), Ar 11Z represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. 11 - represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the viewpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, or a sulfinate ion is preferred. 21 , Ar 22 each independently represents an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group each independently has 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the alkyl group has 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. -represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred. 31 , R 32 , R 33 each independently represents an aryl group, alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, and is preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the carbon number of the alkyl group is independently 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the carbon number of the alkyl group is 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

[0261] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0262] The photoacid generator is preferably used in an amount of 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, even more preferably 0.5 to 10 mass %, still more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.2 mass %, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range. It is also preferable to use a sensitizer in combination in order to impart photosensitivity to a desired light source.

[0263] <Solvent> The resin composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0264] 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 alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-eth Preferred examples of the cypropionic acid alkyl esters include methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0265] Suitable examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0266] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0267] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0268] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0269] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0270] Preferred examples of the ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0271] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0272] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0273] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more of them, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0274] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method.

[0275] The resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types of solvents are contained, the total amount thereof is preferably within the above range.

[0276] <Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Examples of base generators that are preferable for the resin composition of the present invention include a thermal base generator and a photobase generator. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator according to the present invention is not particularly limited, and known base generators can be used.Known base generators include, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, etc. Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3). [ka]

[0277] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom. 1 and Rb 2 cannot be hydrogen atoms at the same time. 1 , Rb 2 and Rb 3None of the above has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, this does not apply to cases in which the bonded carbon atom is a carbon atom that forms a carbonyl group, that is, when the bonded carbon atom forms an amide group together with the nitrogen atom.

[0278] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 At least one of these preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which two monocyclic rings are condensed. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0279] More specifically, Rb 1 and Rb 2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 Rb may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. 1 and Rb 2is particularly preferably a linear, branched or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0280] Rb 3 Examples of the group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and more preferably having 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. 3 may further have a substituent within the range in which the effects of the present invention are exhibited.

[0281] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2). [ka]

[0282] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as: Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and may have a substituent within the range in which the effects of the present invention can be achieved. 13 is preferably an arylalkyl group.

[0283] Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

[0284] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

[0285] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [ka]

[0286] Rb 11 and Rb 12 is Rb in formula (B1-1). 11 and Rb 12 is synonymous with. Rb 15 and Rb 16 represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

[0287] [ka]

[0288] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. N1 and R N2 each independently represents a monovalent organic group.

[0289] In this specification, the term "linking chain" refers to an atomic chain on a path connecting two atoms or atomic groups to be linked, which links these objects with the shortest distance (the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group, has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4. [ka]

[0290] The number of carbon atoms in L in formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly proceeding with the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0291] The base generator also preferably contains a compound represented by the following formula (N1). [ka]

[0292] In formula (N1), R N1 and R N2 each independently represents a monovalent organic group; R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0293] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that is the shortest path between the two carbonyl groups in the formula.

[0294] In formula (N1), R N1 and R N2 R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. N1 and R N2 When an aliphatic hydrocarbon group is used as the alkyl group, the generated base has high basicity, which is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0295] R N1 and R N2Examples of the aliphatic hydrocarbon group constituting the above include a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group. The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The group relating to the combination of the chain alkyl group and the cyclic alkyl group preferably has a carbon number of 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group relating to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. Among them, from the viewpoint of increasing the boiling point of the decomposition product base described later, R N1 and R N2 is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation in which importance is placed on adhesion when laminating with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0296] R N1 and R N2may be linked together to form a cyclic structure. In forming the cyclic structure, an oxygen atom or the like may be included in the chain. N1 and R N2 The cyclic structure formed by may be a single ring or a condensed ring, but is preferably a single ring. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring, and is preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring.

[0297] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

[0298] The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and preferably includes a protecting group which is decomposed by an acid.

[0299] Specific examples of the protective group include linear or cyclic alkyl groups, or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specific examples of such groups include methyloxymethyl (MOM) and ethyloxyethyl (EE). Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0300] The divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. It is more 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 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0301] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups relating to a combination of a linear alkylene group and a cyclic alkylene group, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. The group relating to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms.

[0302] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and still more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, and more preferably has 1 to 4 C═C bonds, and even more preferably has 1 or 2 C═C bonds. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0303] Examples of the base generator include the following, but the present invention is not limited thereto.

[0304] [ka]

[0305] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0306] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0307] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0308] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0309] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0310] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound, and the like.

[0311] [Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of JP-A-2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, compounds described in paragraphs 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0312] [ka]

[0313] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0314] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0315] In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

[0316] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By making it equal to or more than the lower limit, the adhesion between the pattern and the metal layer becomes good, and by making it equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be of only one type, or of two or more types. When two or more types are used, the total is preferably within the above range.

[0317] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor, which makes it possible to effectively inhibit migration of metal ions originating from the metal layer (metal wiring) into the film.

[0318] The migration inhibitor is not particularly limited, but includes compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0319] Alternatively, an ion trapping agent that traps anions such as halogen ions can be used.

[0320] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of these compounds are incorporated herein by reference.

[0321] Specific examples of the migration inhibitor include the following compounds. Among these, from the viewpoints of breaking elongation and adhesion to a metal or resin layer, it is preferable that the migration inhibitor contains any one of tetrazole, 5-aminotetrazole, and M-4 below.

[0322] [ka]

[0323] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition of the present invention.

[0324] The migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, the total amount is preferably within the above range. For example, from the viewpoints of breaking elongation and adhesion to a metal or resin layer, it is preferable to use tetrazole and the above M-4.

[0325] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

[0326] Specific examples of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso -1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP2015-127817A and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469A can also be used, the contents of which are incorporated herein by reference.

[0327] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, based on the total solid content of the resin composition of the present invention.

[0328] The polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0329] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger in order to reduce the performance change over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable, and a secondary amine, a tertiary amine, and an ammonium salt are more preferable. Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, aniline derivatives having a hydroxyl group and / or an ether bond, etc. When the acid scavenger has an onium structure, it is preferred that the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0330] Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo 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]undeca-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having 2-oxoalkyl groups, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the acid scavenger having a pyridine structure include pyridine and 4-methylpyridine. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, etc. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline, etc.

[0331] 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 (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, isobutyl ... ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

[0332] These acid scavengers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger. When it contains an acid scavenger, the content of the acid scavenger is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0333] The ratio of the acid generator to the acid scavenger is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time until heat treatment after exposure, the molar ratio is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and further preferably 7.0 to 150.

[0334] <Urea compounds, carbodiimide compounds, isourea compounds> From the viewpoint of breaking elongation and adhesion to a metal or resin layer, 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 compound, etc."). Examples of the urea compound include the compound represented by the following formula (1-1), examples of the carbodiimide compound include the compound represented by the following formula (1-2), and examples of the isourea compound include the compound represented by the following formula (1-3). [ka]

[0335] In the formula (1-1), the formula (1-2) or the formula (1-3), R 11 and R 12 each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent; R 21 and R 22 each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent; R 31 and R 32 each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent; R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. In formula (1-1), R 11 and R 12are each independently preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having, as a substituent, at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. R 11 and R 12 The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in the formula (I) is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and more preferably an ethyl group, an isopropyl group, a t-butyl group or a cyclohexyl group.

[0336] In formula (1-1), R 11 and R 12 may each independently be an aliphatic hydrocarbon group having 2 to 7 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above-mentioned substituents, but an embodiment having only one of the above-mentioned substituents is also one of the preferred embodiments of the present invention.

[0337] In formula (1-2), R 21 and R 22 each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. In formula (1-2), R 21 and R 22 is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. In formula (1-2), R 21 and R 22 Preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in the above formula are respectively represented by the following formula: 11 and R 12This is similar to that shown in the explanation of .

[0338] In formula (1-3), R 31 and R 32 is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. In formula (1-3), R 31 and R 32 Preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in the above formula are respectively represented by the following formula: 11 and R 12 This is similar to that shown in the explanation of .

[0339] In formula (1-3), R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, is more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and is more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. In formula (1-3), R 33 As the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group is preferable, and an ethyl group is more preferable.

[0340] Specific examples of the urea compound include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0341] The total content of the urea compounds and the like is preferably from 0.1 to 10.0 parts by mass, more preferably from 0.5 to 8.0 parts by mass, and even more preferably from 1.0 to 6.0 parts by mass, relative to 100 parts by mass of the specific resin. The urea compounds etc. may be used alone or in combination of two or more. When two or more urea compounds etc. are used in combination, the total content thereof is preferably within the above-mentioned range.

[0342] <Other additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, it is possible to adjust the properties of the film, etc. These components can be found, for example, in the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of US Patent Application Publication No. 2013 / 0034812), and in paragraphs 0101-0104, 0107-0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein. When these additives are incorporated, the total amount is preferably 3 mass% or less of the solid content of the resin composition of the present invention.

[0343] [Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0344] By adding a surfactant to the photosensitive resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

[0345] Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, and Megafac R30 (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, and Fluorad FC4432 (all manufactured by 3M Corporation). Examples of the fluorine-based surfactant include Surflon S-382, 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, and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A and the compounds described in paragraphs 0117 to 0132 of JP2011-132503A can also be used, the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant. Specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein by reference. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka]

[0346] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. The fluorine-based surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in a side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. In addition, examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0347] The fluorine content in the fluorosurfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the coating film thickness and liquid saving properties, and also has good solubility in the composition.

[0348] Examples of silicone 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 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Co., Ltd.), and the like.

[0349] Examples of hydrocarbon surfactants include Paionin A-76, Newkalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, Paionin P-4050-T, and the like (all manufactured by Takemoto Oil Co., Ltd.).

[0350] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfin E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0351] Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0352] Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

[0353] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0354] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

[0355] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0356] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be one type or two or more types. When the higher fatty acid derivative is two or more types, the total is preferably within the above range.

[0357] [Thermal Polymerization Initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. The addition of the thermal radical polymerization initiator can also advance the polymerization reaction of the resin and the polymerizable compound, thereby further improving the solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0358] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0359] When a thermal polymerization initiator is contained, the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, and further preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0360] [Inorganic particles] The resin composition of the present invention may contain inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0361] The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, further preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurements are difficult, centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method can also be used.

[0362] [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbing agents. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based 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-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0363] Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0364] In the present invention, the above-mentioned various ultraviolet absorbents may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid mass of the composition of the present invention.

[0365] [Organotitanium Compounds] The resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0366] Usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among them, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability of the resin composition and provide a good curing pattern.Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc. II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate.

[0367] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0368] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0369] [Antioxidants] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation property of the cured film and the adhesion to the metal material can be improved. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Examples of preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the site (ortho position) adjacent to the phenolic hydroxyl group are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as the antioxidant, a compound having a phenol group and a phosphite group in the same molecule is also preferred. In addition, as the antioxidant, a phosphorus-based antioxidant can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA CORPORATION). In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant, the contents of which are incorporated herein by reference. In addition, the composition of the present invention may contain a latent antioxidant as necessary. Examples of latent antioxidants include compounds in which the site functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant when heated at 100 to 250° C. or heated at 80 to 200° C. in the presence of an acid / base catalyst, causing the protecting group to be removed.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Laid-Open No. 2017-008219, the contents of which are incorporated herein by reference. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Corporation). Preferred examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

[0370] [ka]

[0371] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), R 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

[0372] The compound represented by formula (3) suppresses the oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin, and also suppresses metal oxidation by preventing rust on metal materials.

[0373] Since it can act on resin and metal materials simultaneously, k is preferably an integer of 2 to 4. 7Examples of the group include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, from the viewpoints of solubility in a developer and metal adhesion, it is preferable to have an alkyl ether group or -NH-, and from the viewpoints of interaction with a resin and metal adhesion due to metal complex formation, -NH- is more preferable.

[0374] Examples of the compound represented by general formula (3) include, but are not limited to, the following structures.

[0375] [ka]

[0376] [ka]

[0377] [ka]

[0378] [ka]

[0379] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By making the amount added 0.1 parts by mass or more, it is easy to obtain the effect of improving the elongation characteristics and adhesion to metal materials even in a high-temperature and high-humidity environment, and by making the amount added 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, by interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0380] [Anti-aggregation agent] The resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Examples of the anti-aggregation agent include sodium polyacrylate.

[0381] In the present invention, the anti-aggregating agent may be used alone or in combination of two or more kinds. The composition of the present invention may or may not contain an anti-agglomerating agent. When the composition of the present invention contains an anti-agglomerating agent, the content of the anti-agglomerating agent is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.02% by mass to 5% by mass, relative to the total solid content mass of the composition of the present invention.

[0382] [Phenol compounds] The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0383] In the present invention, the phenolic compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. When it does contain a phenolic compound, the content of the phenolic compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[0384] [Other polymer compounds] Examples of the other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified by introducing a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group.

[0385] In the present invention, the other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When the composition of the present invention contains other polymer compounds, the content of the other polymer compounds is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[0386] <Characteristics of resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. 2 / s~12,000mm 2 / s is preferred, 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500 mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it is easy to obtain a highly uniform coating film. 2 If the thickness is more than 12,000 mm / s, it is easy to apply the film to a thickness required for an interlayer insulating film for a rewiring layer, for example. 2 / s or less, a coating film with excellent surface condition can be obtained.

[0387] <Restrictions on substances contained in resin compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

[0388] The metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass, from the viewpoint of insulation. Metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, the total of these metals is preferably within the above range.

[0389] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials having a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

[0390] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, those existing in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0391] A conventionally known container can be used as the container for the resin composition of the present invention. In addition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six-layer resins or a bottle with a seven-layer structure made of six types of resins as the container for the purpose of suppressing impurities from being mixed into the raw materials or the resin composition of the present invention. Examples of such containers include the container described in JP 2015-123351 A.

[0392] <Cured product of resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The resin composition is preferably cured by heating, and the heating temperature is more preferably within the range of 120°C to 400°C, even more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as a film, a rod, a sphere, or a pellet. In the present invention, the cured product is preferably in the form of a film. In addition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance, or internal stress, and imparting a heat dissipation function, by pattern processing of the resin composition. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The cured product can be used for both thin film and thick film applications. When using a thin film layer, the thickness is preferably 1 to 15 μm, more preferably 2 to 12 μm, and even more preferably 3 to 10 μm. When a thick layer is used, the thickness is preferably from 15 to 50 μm, more preferably from 15 to 40 μm, and even more preferably from 15 to 30 μm. The shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated by the following formula. Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) x 100

[0393] <Characteristics of the cured resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The breaking elongation of the cured product of the 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 product of the 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.

[0394] <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 a conventionally known method. The mixing can be performed by using a stirring blade, a ball mill, or by rotating the tank itself. The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

[0395] In addition, it is preferable to perform filtration using a filter in order to remove foreign matter such as dust and fine particles in the resin composition of the present invention. The filter pore size may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene). The filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As an example of a connection mode, an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage may be connected in series. In addition, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be applied may 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 a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used. Furthermore, after filtration using a filter, the resin composition filled in the bottle may be subjected to a step of placing it under reduced pressure and degassing it. EXAMPLES

[0396] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are by weight unless otherwise specified.

[0397] <Synthesis Example 1: Synthesis of Polymer B-1> 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was placed in a 2-liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generation caused by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours. Next, under ice cooling, 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 while 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 while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the precipitate was filtered and then vacuum dried to obtain a powdered polymer B-1. The weight average molecular weight (Mw) of this polymer B-1 was measured and found to be 20,000.

[0398] <Synthesis Example 2: Synthesis of Polymer B-2> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at 60°C for 18 hours to produce the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C and 16.12 g (135.5 mmol) of SOCl2 was added over 2 hours while maintaining the temperature at -5±2°C. Next, a solution of 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 2 hours while adjusting the temperature to the range of -5 to 0° C. The reaction mixture was reacted at 0° C. for 1 hour, after which 70 g of ethanol was added and stirred at room temperature for 1 hour. The polyimide precursor was then precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, and stirred again in 4 liters of water for 30 minutes and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45° C. for 2 days to obtain polymer B-2. The weight average molecular weight (Mw) of this polymer B-2 was measured and found to be 22,000.

[0399] <Synthesis Example 3: Synthesis of Polymer B-3> 28.0g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200mL of N-methylpyrrolidone with stirring. Then, 25.0g of 4,4'-oxydibenzoyl chloride (8.00g) was added dropwise over 10 minutes while keeping the temperature at 0-5°C, and stirring was continued for 60 minutes. Then, 25.0g of pyridine was added, and 5.8g of methacrylic acid chloride was added dropwise over 10 minutes while keeping the temperature at 0-5°C, and stirring was continued for 60 minutes. Then, 0.15 g of 2,6-di-tert-butyl-p-cresol was added to the resulting reaction mixture. 6 L of water was added to precipitate the polybenzoxazole precursor, and the precipitate (water-polybenzoxazole precursor mixture) was stirred at a speed of 200 rpm for 15 minutes. The precipitate after stirring was filtered and dried under reduced pressure at 45° C. for 3 days to obtain a polybenzoxazole precursor (polymer B-3). This polybenzoxazole precursor (polymer B-3) had a weight average molecular weight of 3,250 and a number average molecular weight of 9,800.

[0400] <Synthesis Example 4: Synthesis of Polymer B-4> Polymer B-4 was obtained by carrying out a reaction in the same manner as in Synthesis Example 1, except that a mixture of 73.5 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 77.5 g of 4,4'-oxydiphthalic dianhydride was used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride in Synthesis Example 1. The weight average molecular weight (Mw) of this polymer B-4 was measured and found to be 22,000. 【04...

Claims

1. a film-forming step of applying a photosensitive resin composition containing a precursor of a cyclized resin, a photopolymerization initiator, and a polymerizable compound containing four or more radically polymerizable groups onto a substrate to form a film; an exposure step of selectively exposing the film to light; a developing step of developing the exposed film with a developer to form a pattern; a treatment step of contacting the pattern with a treatment liquid; and a heating step of heating the pattern after the processing step, the treatment liquid contains at least one compound selected from the group consisting of a base and a base generator, The processing liquid is a solvent different from the solvent contained in the developer, and contains at least one compound selected from the group consisting of a base and a base generator. A method for producing a cured product.

2. The method for producing a cured product according to claim 1 , wherein the treatment liquid is a rinse liquid.

3. The method for producing a cured product according to claim 1 or 2, wherein the treatment step is a rinsing step of cleaning the pattern with the treatment liquid.

4. The method for producing a cured product according to any one of claims 1 to 3, wherein the developer contains an organic solvent in an amount of 50% by mass or more based on the total mass of the developer.

5. The method for producing a cured product according to any one of claims 1 to 4, wherein the base comprises an organic base.

6. The method for producing a cured product according to any one of claims 1 to 5, wherein the base comprises a secondary amine or a tertiary amine.

7. The method for producing a cured product according to any one of claims 1 to 6, wherein the precursor of the cyclized resin is a polyimide precursor containing a repeating unit represented by the following formula (2): [Formula 1] In formula (2), A １ and A ２ each independently represents an oxygen atom or -NH-; R １１１ represents a divalent organic group; R １１５ represents a tetravalent organic group; R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group.

8. The method for producing a cured product according to any one of claims 1 to 7, wherein the heating step is a step of promoting cyclization of the precursor of the cyclized resin in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator through heating.

9. The method for producing a cured product according to any one of claims 1 to 8, wherein the heating temperature in the heating step is 120 to 230°C.

10. The method for producing a cured product according to any one of claims 1 to 9, wherein the developing step is a step of supplying the developer to the exposed film by showering or a step of continuously supplying the developer to the exposed film.

11. The method for producing a cured product according to any one of claims 1 to 10, wherein the development in the developing step is negative development.

12. A method for producing a laminate, comprising repeating the method for producing a cured product according to any one of claims 1 to 11 multiple times.

13. The method for producing a laminate according to claim 12, further comprising a metal layer forming step of forming a metal layer on the cured product between the methods for producing the cured product which are performed multiple times.

14. A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of claims 1 to 11, or the method for producing a laminate according to claim 12 or 13.

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