TW202043295A - Cured film production method, resin composition, cured film, laminate body production method, and semiconductor device manufacturing method - Google Patents

Abstract

This cured film production method involves: a step for forming a film by applying to a substrate a resin composition that contains a radical polymerizable monomer and at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and a step for thermally curing the film in an environment in which the partial pressure of oxygen is 6-150 Pa. A resin composition, cured film, laminate body production method, and semiconductor device manufacturing method are also provided.

Description

Method for manufacturing cured film, resin composition, cured film, method for manufacturing laminate, and method for manufacturing semiconductor element

The present invention relates to a production of a cured film using a resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer method. In addition, the present invention relates to a method of manufacturing a resin composition, a cured film, a laminate, and a method of manufacturing a semiconductor element.

Cyclized and hardened resins such as polyimide resins and polybenzoxazole resins have excellent heat resistance and insulation properties, and are therefore suitable for various applications. The use is not particularly limited, but if a semiconductor element for actual mounting is taken as an example, it can be used as a material for an insulating film or a sealing material or the use of the protective film. In addition, it is also used as a base film or cover layer of a flexible substrate.

Such polyimide resins and the like generally have low solubility in solvents. Therefore, a method of dissolving in a solvent in a state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor is often used. Thereby, excellent operability can be achieved, and it can be applied to a substrate or the like in various forms for processing when manufacturing each product as described above. After that, the cyclized polymer precursor can be heated to form a hardened product. In addition, when heating the cyclized polymer precursor, in order to prevent oxidation of the substrate, the heating is performed in an atmosphere in which the oxygen concentration is reduced, such as in a nitrogen atmosphere.

For example, Patent Document 1 describes that a photosensitive polyimide precursor layer is heated at 200°C or higher and 350°C or lower in an environment with an oxygen concentration of 50 ppm or less to form a photosensitive polyimide resin layer. . In addition, Patent Document 2 describes that a resin film selected from a photosensitive polyimide precursor or a photosensitive polybenzoxazole precursor is heat-treated in a nitrogen atmosphere, and then heat-treated in an atmosphere containing oxygen The content. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2010-054451 A [Patent Document 2] JP 2004-031564 A

When a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor is used to produce a cured film, it is desirable to further reduce the heating and curing temperature. However, as the heating and curing temperature is lowered, the mechanical properties such as ductility of the obtained cured film tend to decrease. In the inventions described in Patent Documents 1 and 2, it is also difficult to produce a cured film that meets the level required in recent years.

Therefore, an object of the present invention is to provide a method for manufacturing a cured film, a method for manufacturing a resin composition, a cured film, a laminate, and a method for manufacturing a semiconductor element with excellent mechanical properties.

According to the research of the present inventors, it was found that by using as a resin composition, at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer The resin composition of the body, the film obtained by using the resin composition is heated and cured in an atmosphere with an oxygen partial pressure of 6 to 150 Pa, and a cured film with excellent mechanical properties can be obtained, thus completing the present invention. The present invention provides the following.

<1> A method for manufacturing a hardened film, which includes: Applying a resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoazole precursor and a radical polymerizable monomer to the substrate to form a film; as well as The step of heating and curing the film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa. <2> The method for producing a cured film as described in <1>, wherein the pressure of the atmosphere in the heat curing step is 0.08 to 0.12 MPa. <3> The method for producing a cured film as described in <1> or <2>, wherein the film is heated to 170 to 350°C in the heat curing step. <4> The method for producing a cured film as described in any one of <1> to <3>, wherein the step of exposing the film and the step of exposing the film between the step of forming the film and the step of heat curing The film is developed. <5> The method for producing a cured film according to any one of <1> to <4>, wherein the substrate to which the resin composition is applied is a metal substrate or a substrate containing a metal layer. <6> The method of manufacturing a cured film as described in any one of <1> to <5>, which is a method of manufacturing a cured film for an insulating layer. <7> A resin composition comprising at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a radical polymerizable monomer, This resin composition is used in the manufacturing method of the cured film described in any one of <1> to <6>. <8> A cured film obtained from the resin composition described in <7>. <9> A method for manufacturing a laminate, comprising a step of forming a cured film by the method of manufacturing a cured film according to any one of <1> to <6> and a step of forming a metal layer on the surface of the cured film. <10> A method of manufacturing a semiconductor element, comprising the method of manufacturing the cured film described in any one of <1> to <6> or the method of manufacturing the laminate described in <9>. [Invention Effect]

According to the present invention, it is possible to provide a method for manufacturing a cured film having excellent mechanical properties, a method for manufacturing a resin composition, a cured film, a laminate, and a method for manufacturing a semiconductor element.

Hereinafter, the content of the present invention will be described. In addition, in this specification, "-" means that the numerical value described before and after it is used as the meaning of the range included as a lower limit and an upper limit.

The description of the constituent elements in the present invention described below may be performed based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the label of the group (atomic group) in this specification, the label system that does not describe substituted and unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, active rays or radiations such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers are usually cited. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, the term "step" is not only an independent step, but even when the law is clearly distinguished from other steps, if the desired effect of the step can be achieved, it is included in this term. Unless otherwise specified, the physical property value in the present invention is set to a value of a temperature of 23° C. and a pressure of 101325 Pa or less. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are those measured by gel permeation chromatography (GPC measurement), and are defined as styrene conversion values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super can be used as the columns. HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). In this measurement, unless otherwise specified, THF (tetrahydrofuran) is used as the eluent. In addition, unless otherwise specified, the detection is to use a UV ray (ultraviolet) wavelength 254 nm detector. Unless otherwise specified, the temperature in the present invention is set to 23°C.

[Method of manufacturing cured film] The method for producing a cured film of the present invention is characterized by including at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and radical polymerizable monomers. The resin composition is suitable for a step of forming a film on a substrate (film forming step) and a step of heating and curing the above-mentioned film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa (heating curing step).

According to the present invention, a cured film with excellent mechanical properties such as ductility can be formed. Although the detailed reason is not clear, it is speculated that by heating and curing the film in an atmosphere with the predetermined oxygen partial pressure, the amount of oxygen present increases, and the original crosslink density of the radical polymerizable monomer and the polymer precursor decreases slightly. The interaction between the polymer precursors is alleviated, and the resistance to the stress direction is improved. In addition, it is generally believed that the polymerization reaction of radically polymerizable monomers is easily hindered in the presence of oxygen. Therefore, it is considered that when a film obtained by using a resin composition containing a radical polymerizable monomer is heated and cured, a cured film with excellent mechanical properties such as ductility can be obtained when the oxygen partial pressure during heat curing is low, but it is surprising that The heat curing of the film is performed in an atmosphere of the oxygen partial pressure in the above-mentioned range, and the mechanical properties such as ductility of the obtained cured film are improved.

In addition, the oxygen partial pressure at the time of heat curing is in the above-mentioned range, so that the oxidation of the substrate can also be suppressed. Therefore, it is particularly effective when a metal layer or a metal substrate is used as the substrate.

The method of manufacturing the film of the present invention preferably includes a step of exposing the film and a step of developing the exposed film between the step of forming the film (film forming step) and the step of heat curing (heat curing step). That is, it is preferable that the method of manufacturing the film of the present invention includes the following steps (a) to (d). According to this aspect, it is possible to form a pattern of a cured film having excellent mechanical properties such as ductility. The cured film thus formed can be preferably used as an insulating layer. In particular, it can be suitably used as an interlayer insulating film for a rewiring layer. (A) A step of applying a resin composition to a substrate to form a film (film forming step), (B) After the film formation step, the step of exposing the film (exposure step), (C) The step of developing the exposed film (development step), (D) A step of heating and curing the developed film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa (heat curing step).

Hereinafter, each step will be described in detail.

＜Film formation step＞ In the film formation step, a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a radical polymerizable monomer is applied to the substrate And a film is formed. The details of the resin composition will be described later.

The type of substrate can be appropriately determined according to the application. For example, an inorganic substrate, a resin substrate, a resin composite substrate, etc. can be mentioned. Examples of the inorganic substrate include silicon substrates, silicon nitride substrates, polycrystalline silicon substrates, silicon oxide substrates, amorphous silicon substrates, glass substrates, quartz substrates, metal substrates, and the like. Metal layers such as molybdenum, titanium, aluminum, copper, etc. can be formed on the surface of a silicon substrate, a silicon nitride substrate, a polysilicon substrate, a silicon oxide substrate, an amorphous silicon substrate, a glass substrate, and a quartz substrate. Examples of resin substrates include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and polybutylene terephthalate. Phosphorus, polyether ether, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyimide, polyetherimine, polybenzoxazole, polyphenylene sulfide Ether, polycyclic olefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, cross-linked butene Diacid diester, cyclic polyolefin, aromatic ether, maleimide, olefin, cellulose, episulfide compound and other synthetic resin substrates. A metal layer may be formed on the surface of the resin substrate. In the present invention, even when a substrate or a metal substrate having a metal layer is used, it is possible to form a cured film that suppresses the oxidation of the metal and has excellent mechanical properties such as ductility. Therefore, it is particularly effective when such a substrate is used.

As a method of applying the resin composition to the substrate, coating is preferred. Specifically, as applicable methods, there can be exemplified dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the formed film (resin composition layer), the spin coating method, the slit coating method, the spray method, and the inkjet method are more preferable. By adjusting the appropriate solid content concentration or coating conditions according to the method, a film (resin composition layer) of a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method Or spray method, inkjet method, etc. are preferable. In the case of the spin coating method, it can be applied under the conditions of a rotation speed of 500 to 2000 rpm and about 10 seconds to 1 minute, for example.

In the film formation step, after the resin composition is applied to the substrate, drying for removing the solvent may be performed. The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. The drying time is 30 seconds to 20 minutes, preferably 1 to 10 minutes, more preferably 3 to 7 minutes.

<Exposure Step> The method of manufacturing the film of the present invention may include a step of exposing the film (exposure step) after the film formation step. In the exposure step, the film (resin composition layer) is exposed through a mask having a predetermined mask pattern using a stepper exposure machine, a scanning exposure machine, or the like, thereby enabling exposure in a pattern.

The exposure amount is not particularly limited within the range that can harden the film (resin composition layer). For example, it is better to irradiate 100 to 10000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and 200 to 8000 mJ/cm. ² is better. The exposure wavelength can be appropriately set within the range of 190-1000 nm, preferably 240-550 nm. Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) High-pressure mercury lamp, g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm), wide (3 wavelengths of g, h, and i rays), (4) excimer laser, KrF Molecular laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, etc. . Regarding the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained.

<Development step> The manufacturing method of the film of this invention may include the process (development process) of developing the film (resin composition layer) after exposure. By developing, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as the desired pattern can be formed. For example, development methods such as spin immersion, spray, dipping, and ultrasonic waves can be used. The development is performed using a developer. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, it can be used without particular limitation. It is preferable that the developer contains an organic solvent, and it is more preferable that the developer contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula in ChemBioDraw (Chemical Biological Diagram). Regarding the organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid can be suitably mentioned. Ethyl, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (example: methyl alkoxy acetate , Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Esters, etc.)), 3-alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g. 3-methoxy propionate methyl Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate)), 2-Alkoxy-2-Methyl Propionate and 2 -Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example Suitable examples 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as Ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be suitably mentioned, and as aromatic hydrocarbons For example, toluene, xylene, anisole, limonene, etc. can be suitably mentioned, and as the sulfenite, dimethyl sulfene can be suitably mentioned. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. An organic solvent of 50% by mass or more of the developer is preferable, an organic solvent of 70% by mass or more is more preferable, and an organic solvent of 90% by mass or more is more preferable. In addition, 100% by mass of the developer may be an organic solvent.

As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developing solution during development is not particularly limited, and it can usually be performed at 20 to 40°C. After treatment with developer, it can be rinsed. Rinsing is preferably performed with a solvent different from the developer. For example, it may be rinsed with a solvent contained in the resin composition. Preferably, the rinsing time is 5 seconds to 1 minute.

＜Heat hardening step＞ In the heat curing step, the film (the film developed during the exposure step and the development step is included) is heated. The cyclization reaction of the polymer precursor proceeds by heating to obtain a cured film. The heat curing step can be performed by heating the film in a heating chamber, for example.

In the present invention, the film is heated in an atmosphere with an oxygen partial pressure of 6 to 150 Pa. Regarding the upper limit of the oxygen partial pressure in the heating step, for the reason of suppressing the corrosion of the substrate, 120 Pa or less is preferable, 100 Pa or less is more preferable, and 60 Pa or less is more preferable. In addition, regarding the lower limit of the oxygen partial pressure, for the reason that it is easy to obtain a cured film having more excellent ductility and other mechanical properties, 7 Pa or more is preferable, 10 Pa or more is more preferable, and 30 Pa or more is more preferable. In addition, when the film is heated in the heating chamber, the oxygen partial pressure in the heating chamber corresponds to the oxygen partial pressure in the atmosphere of the heating and hardening step.

As a method of adjusting the oxygen partial pressure in the atmosphere of the heating and hardening step to the above range, there can be mentioned a method of replacing the gas in the atmosphere in the heating chamber with an inert gas to adjust the oxygen partial pressure, and reducing the pressure in the heating chamber As for the method of adjusting the oxygen partial pressure, for the reasons of membrane stability, the method of adjusting the oxygen partial pressure by replacing the gas in the atmosphere in the heating chamber with an inert gas is preferable. Examples of the inert gas include nitrogen, helium, argon, and the like.

For the reasons of film stability, the atmosphere pressure of the heating and hardening step is preferably 0.08~0.12 MPa, and more preferably 0.09~0.11 MPa. In addition, when the film is heated in the heating chamber, the pressure in the heating chamber is equivalent to the atmospheric pressure in the heating and hardening step.

In addition, the oxygen concentration in the atmosphere of the heating and hardening step is more than 60 volume ppm and 1500 volume ppm or less. The lower limit is preferably 65 volume ppm or more, more preferably 100 volume ppm or more, and more preferably 500 volume ppm or more. The upper limit is preferably 1400 volume ppm or less, more preferably 1200 volume ppm or less, and more preferably 1000 volume ppm or less. In addition, when the film is heated in the heating chamber, the oxygen concentration in the heating chamber corresponds to the oxygen concentration in the atmosphere of the heating and hardening step.

As the heating temperature (maximum heating temperature) of the film in the heat curing step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is even more preferred, 150°C or higher is even more preferred, and 160°C or higher is more preferred. It is still more preferable, and 170°C or higher is still more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is more preferred, 250°C or less is even more preferred, and 220°C or less is still more preferred. In addition, the heating temperature (maximum heating temperature) of the film is preferably 170 to 350°C. Regarding heating, it is preferable to perform heating at a temperature increase rate of 1-12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be alleviated. The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at the beginning of the step of heating to the highest heating temperature. For example, when the resin composition is applied to a substrate and dried, the temperature of the film (layer) after drying is, for example, gradually from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition It is better to increase the temperature. The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes. In particular, when forming a multilayer laminate, from the viewpoint of the adhesiveness between the layers of the cured film, the film is preferably heated at 180°C to 320°C, and more preferably at 180°C to 260°C. Although the reason is uncertain, it is thought that the reason is as follows. That is, by setting the temperature at this temperature, the ethynyl groups of the polymer precursors between the layers undergo a crosslinking reaction.

Heating can be carried out in stages. As an example, it is possible to perform the treatment before raising the temperature from 25°C to 180°C at 3°C/min, and keeping it at 180°C for 60 minutes, heating it from 180°C to 200°C at 2°C/min, and keeping it at 200°C for 120 minutes step. The heating temperature as the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and further preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the film can be improved by these pretreatment steps. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

The cured film can be manufactured through the above steps. Examples of fields to which the cured film can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, and stress buffer films. In addition to this, a sealing film, a substrate material (base film or cover layer of a flexible printed circuit board, and an interlayer insulating film), or a case where an insulating film for actual mounting use as described above is patterned by etching, and the like can be mentioned. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaki/Supervisor, CMC Technical Library "Polyimide Materials The foundation and development of "Polyimine" issued in November 2011, Japan Polyimide and Aromatic Polymer Research Society/Edition "The latest polyimide basics and applications" NTS, August 2010, etc. In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, the use of molded parts, and the production of protective paints and dielectric layers in electronics, especially microelectronics.

[Method of manufacturing laminate] The method of manufacturing a laminate of the present invention includes a step of forming a cured film by the method of manufacturing a cured film of the present invention (cured film forming step) and a step of forming a metal layer on the surface of the cured film (metal layer forming step).

The type of the metal layer formed on the surface of the cured film is not particularly limited. Existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable , Copper is further preferred. The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited. The thickness of the metal layer is preferably 0.1-50 μm at the thickest part, and more preferably 1-10 μm.

In the manufacturing method of the laminated body of the present invention, after the metal layer forming step, it is also preferable to form a cured film on the surface of the cured film (resin layer) or the metal layer again by the above-mentioned manufacturing method of the cured film of the present invention. In addition, the method for producing a laminate of the present invention may alternately perform the cured film forming step and the metal layer forming step a plurality of times (preferably 2 to 7 times, more preferably 2 to 5 times). In this way, it is possible to manufacture a laminate having a multilayer wiring structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer that alternately laminate plural cured films (resin layers) and metal layers.

[Method of manufacturing semiconductor element] The manufacturing method of the semiconductor element of this invention includes the manufacturing method of the cured film of the said invention, or the manufacturing method of the laminated body of the said invention. As a specific example of the semiconductor element, reference can be made to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1, and these contents are incorporated in this specification.

[Resin composition] Next, the resin composition used in the manufacturing method of the film of this invention is demonstrated.

＜Polymer precursors＞ The resin composition of the present invention comprises a polymer precursor selected from polyimide precursors and polybenzoxazole precursors. In view of the fact that the effect of the present invention is easily obtained more remarkably, the polymer precursor-based polyimide precursor used in the present invention is preferred.

A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。<<Polyimine precursor>> As the polyimine precursor, it is preferable to include a structural unit represented by the following formula (1). By using this structure, a composition with more excellent film strength can be obtained. [化1]

A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group.

A ¹ and A ² are each independently an oxygen atom or NH, and an oxygen atom is preferred.

＜＜＜R ¹¹¹ ＞＞＞ R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups containing these combinations, linear aliphatic groups having 2 to 20 carbon atoms A group, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a group including a combination of these are preferred. The aromatic group of 6 to 20 is more preferable. R ¹¹¹ is preferably derived from diamine. Examples of the diamine 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, the diamine includes a straight-chain aliphatic group with 2 to 20 carbons, a branched or cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a group containing these combinations Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.

[化2]

In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHCO- and groups of these combinations are preferred, single bonds, selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(=O)-, The groups in -S- and -SO ₂ -are more preferably selected from the group including -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C(CH _{3) 2} - group of the divalent group is further preferred.

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenyl sulfide and 3,3-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2-dimethylbiphenyl), 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)supplement, bis(4-amino-3-hydroxyphenyl)supplement, 4 ,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4 -(3-Aminophenoxy)phenyl] ash, bis[4-(2-aminophenoxy)phenyl] ash, 1,4-bis(4-aminophenoxy)benzene, 9 ,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 1,3-bis(4-aminophenoxy) Benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diamino Diphenylmethane, 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) sulfide, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3,3 ',5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy) ethyl methacrylate), 2 ,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p Phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-di Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluoro Toluene, 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, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-tri Fluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3-amino-5 -Trifluoromethylphenoxy) diphenyl sulfide, 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 At least one diamine among 5',6,6'-hexafluorotolidine and 4,4'-diaminotetrabiphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[化3]

Moreover, as a preferable example, the diamine which has at least two alkylene glycol units in the main chain can also be mentioned. It is preferable to combine diamines containing two or more of ethylene glycol chains and propylene glycol chains or both in one molecule, and it is more preferable to combine diamines containing no aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethyl (Oxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but not limited For these. The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.

[化4]

In the above, x, y, and z are average values.

From the viewpoint of the flexibility of the cured film obtained, R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. Among them, Ar ^{0 is} each independently an aromatic hydrocarbon group (the carbon number is preferably 6-22, more preferably 6-18, particularly preferably 6-10), and phenylene is preferred. L ⁰ represents a single bond, selected from aliphatic hydrocarbon groups having 1 to 10 carbons which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) ₂ -,- NHCO- and the group in the combination of these. The definition of the preferred range is the same as the above A.

R⁵⁰ ~R⁵⁷ 分別獨立地為氫原子、氟原子或1價有機基團，R⁵⁰ ~R⁵⁷ 中的至少一個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價有機基團時，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化6]

R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by formula (61) is more preferable. [化5]

R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl . ^Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably carbons). Numbers 1 to 6) fluorinated alkyl groups, etc. [化6]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, fluoromethyl, difluoromethyl, or trifluoromethyl.

As the diamine compound imparting the structure of formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.

R¹¹² 的定義與A相同，較佳範圍亦相同。<<< R ¹¹⁵ >>> formula R ¹¹⁵ (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. [化7]

The definition of R ^{112 is} the same as that of A, and the preferred range is also the same.

R¹¹⁵ 表示4價有機基團。R¹¹⁵ 的定義與式（1）的R¹¹⁵ 相同。Regarding the tetravalent organic group represented by R ¹¹⁵ in the formula (1), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [化8]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same as defined in formula (1) is R ^115.

Specific examples of tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 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 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be mentioned as a preferable example. [化9]

<<<R ¹¹³ and R ¹¹⁴ >>> In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ is preferably a repeating unit containing a radical polymerizable group, and it is more preferred that both of them contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryloyl group, a group represented by the following formula (III), and the like.

[化10]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbons, -CH ₂ CH(OH)CH ₂ -or a (poly)oxyalkylene having 4 to 30 carbons (as an alkylene group, carbon The number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3; the repeating number is preferably from 1 to 12, more preferably from 1 to 6 and particularly preferably from 1 to 3). In addition, (poly)alkylene oxide means alkylene oxide or polyalkylene oxide. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are Better. Particularly preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylene group.

As a preferred embodiment of the polyimide precursor in the present invention, the monovalent organic group of R ¹¹³ or R ¹¹⁴ may include 1, 2 or 3 acid groups, preferably one acid group The aliphatic group, aromatic group and aralkyl group, etc. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is more preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developer can be preferably used. From the viewpoint of solubility to an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The alkyl group preferably has 1 to 30 carbon atoms (when it is cyclic, it is 3 or more). The alkyl group may be any of linear, branched, and cyclic. Examples of straight-chain or branched-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Diacyl, dicyclohexyl and pinenyl (pinenyl). In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred.

The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a sulphur ring, a pentane ring, Indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, terylene ring, etc.) or substituted Or unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring 𠯤 ring, pyrimidine ring, pyrimidine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinidine ring, quinoline ring, phthalo ring, naphthyridine ring , Quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, Kouyamaguchi ring, phenanthrene ring, Brown ring or brown ring).

In addition, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, but is actually 50% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, the aliphatic group having a siloxane structure and the structural unit represented by formula (1) can be copolymerized. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

A¹¹ 及A¹² 表示氧原子或NH，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一者係包含自由基聚合性基團之基團為較佳，自由基聚合性基團為更佳。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A) or (1-B). [化11]

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, in R ¹¹³ and R ¹¹⁴ At least one of is preferably a group containing a radical polymerizable group, more preferably a radical polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1). The same meaning as R ¹¹² in the preferred range of R of formula (5) ^112, wherein the oxygen atoms. In the formula (1-A), the bonding position of the carbonyl group on the benzene ring is preferably 4, 5, 3', 4'. In formula (1-B), 1, 2, 4, and 5 are preferred.

In the polyimide precursor, the structural unit represented by the formula (1) may be one type or two or more types. Furthermore, it may contain structural isomers of the structural unit represented by formula (1). Moreover, in addition to the structural unit of the above-mentioned formula (1), the polyimide precursor may contain other kinds of structural units.

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total structural unit can be exemplified, further 70 mol% or more, especially 90 mol% or more, represented by formula (1) The polyimide precursor of the constituent unit. As the upper limit, it is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5-3.5, more preferably 2-3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with a diamine. In the production method of the polyimide precursor, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When the polyimide precursor is manufactured, it is preferable to include a step of separating out solids. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation.

R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團。<<Polybenzoxazole precursor>> The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2). [化12]

R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. Divalent organic groups include aliphatic groups (with carbon numbers of 1-24, preferably, 1-12, particularly preferably, 1-6) and aromatic groups (with 6-22 carbons, 6 ～14 is more preferable, and 6-12 are particularly preferable) at least one group is preferable. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ in the above formula (1). As the aforementioned aliphatic group, a straight-chain aliphatic group is preferred. Preferably, R ^{121 is} derived from 4,4'-oxobenzyl chloride. In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same definitions as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

In addition to the structural unit of the above-mentioned formula (2), the polybenzoxazole precursor may contain other kinds of structural units. From the viewpoint of being able to suppress the occurrence of warpage of the cured film accompanying ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit.

Z具有a結構和b結構，R^1s 為氫原子或碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^2s 為碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^3s 、R^4s 、R^5s 、R^6s 中的至少一個為芳香族基（較佳為碳數6～22，更佳為碳數6～18，特佳為碳數6～10），剩餘部分為氫原子或碳數1～30（較佳為碳數1～18，更佳為碳數1～12，特佳為碳數1～6）的有機基團，且可以分別相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。Z部分中，較佳為a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。[化13]

Z has a structure and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), R ^2s is 1 to 10 carbons Hydrocarbyl group (preferably carbon number 1 to 6, more preferably carbon number 1 to 3), at least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group (preferably carbon number 6 to 22, More preferably, the carbon number is 6 to 18, particularly preferably the carbon number is 6 to 10), and the remainder is a hydrogen atom or a carbon number of 1 to 30 (preferably carbon number 1 to 18, more preferably carbon number 1 to 12, especially It is preferably an organic group having 1 to 6 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. In the Z part, it is preferable that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. In addition, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by the gel permeation chromatography method generally used. By setting the above-mentioned molecular weight to the above-mentioned range, it is possible to reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and to suppress the warpage and improve the solubility.

When the precursor contains the diamine residue represented by the formula (SL) as another type of structural unit, it also includes the tetracarboxylic acid remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride in view of improving the alkali solubility An acid residue is preferable as a structural unit. As an example of these tetracarboxylic acid residues, the example of R ¹¹⁵ in Formula (1) is mentioned.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the polymer precursor in the resin composition of the present invention relative to the total solid content of the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass % Or more is more preferable, 60 mass% or more is still more preferable, and 70 mass% or more is still more preferable. Furthermore, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, and even more preferably 98% by mass or less. 95% by mass or less is more preferable. The resin composition of the present invention may include only one type of polymer precursor, or may include two or more types. When two or more are contained, the total amount is preferably in the above range.

＜Free radical polymerizable monomer＞ The resin composition of the present invention contains a radical polymerizable monomer. As the radical polymerizable monomer, a compound having radical polymerizable properties can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. The radical polymerizable group is preferably a (meth)acryloyl group.

The number of radically polymerizable groups in the radically polymerizable compound may be one or two or more. The radically polymerizable compound preferably has two or more radically polymerizable groups, with three The above is better. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radical polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the resin composition of the present invention preferably contains at least one bifunctional or more radical polymerizable monomer containing two or more polymerizable groups, and at least one trifunctional or more radical polymerizable monomer Sexual monomer is better. In addition, it may be a mixture of a bifunctional radical polymerizable monomer and a trifunctional or more radical polymerizable monomer. In addition, the number of functional groups of a radically polymerizable monomer represents the number of radically polymerizable groups per molecule.

Specific examples of radical polymerizable monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, and amides. Types, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or toluene Substitution reactants of unsaturated carboxylic acid esters or amides having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, reference can be made to the description in paragraphs 0113 to 0122 of JP 2016-027357 A, and these contents are incorporated in this specification.

In addition, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl erythritol tri (Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) Base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohol Compounds in which ethylene oxide or propylene oxide is added and then (meth)acrylated, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Application Publication No. 51-037193 The (meth)acrylate urethanes described in Japanese Patent Application Publication No. 48-064183, Japanese Patent Application Publication No. 49-043191, Japanese Patent Application Publication No. 52-030490, and polyester acrylates, Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. In addition, a polyfunctional (meth)acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid can also be mentioned. In addition, as preferred radical polymerizable monomers other than those described above, it is also possible to use those described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc. , And has two or more groups containing ethylenically unsaturated bonds or cardo resins. Furthermore, as other examples, there are specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Publication No. 02- Vinylphosphonic acid compounds described in 025493 Publication. In addition, compounds containing perfluoroalkyl groups described in JP 61-022048 A can also be used. Furthermore, it is also possible to use those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

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

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable monomers. This compound is added to a polyfunctional alcohol It is a compound formed by (meth)acrylate esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a radical polymerizable monomer, and these contents are incorporated in this specification.

As a radically polymerizable monomer, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product) It is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd., dineopentylene pentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dineopentyl erythritol hexa(meth)acrylate (as a commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin- Nakamura Chemical Co., Ltd. (manufactured by Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As a commercially available product of a radical polymerizable monomer, for example, SR-494 manufactured by Sartomer Company, Inc. is a 4-functional acrylate having 4 ethoxy chains, and SR-494 is a 4 ethyleneoxy chain. 2-functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentyloxy chains, as having 3 TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, three-functional acrylate of a isobutoxy chain NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA -306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), M-306 (manufactured by TOAGOSEI CO., Ltd.) Wait.

As a radically polymerizable monomer, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Urethane acrylates, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have epoxy resins. Urethane compounds with an ethane-based skeleton are also preferred. Furthermore, as a radically polymerizable monomer, it is also possible to use those described in JP 63-277653 A, JP 63-260909 A, and JP 01-105238 having an amino group in the molecule. Structure or sulfide structure compound.

The radically polymerizable monomer may be a compound having an acid group such as a carboxyl group and a phosphoric acid group. Among the radically polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred. The unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group The compound is better. Particularly preferably, among the compounds having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with the non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is a compound of neopentylerythritol and/or dineopentaerythritol. As a commercially available product, for example, M-510, M-520, etc. are mentioned as polyacid-modified acrylic oligomer manufactured by TOAGOSEI CO., Ltd.. The preferred acid value of the radical polymerizable monomer having an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the radically polymerizable monomer is within the above-mentioned range, it will have excellent manufacturing and handling properties, and will also have excellent developability. In addition, the polymerizability is also good.

From the viewpoint of suppressing the warpage accompanying the control of the modulus of elasticity of the cured film, as the radical polymerizable monomer, the resin composition of the present invention can preferably use a monofunctional radical polymerizable monomer. As a monofunctional radical polymerizable monomer, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butane Oxyethyl (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, etc. (meth) Acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic triene Allyl compounds such as propyl ester, etc. As a monofunctional radical polymerizable monomer, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

The content of the radically polymerizable monomer is preferably 1 to 60% by mass relative to 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 more preferably 30% by mass or less. The radically polymerizable monomer may be used singly or in combination of two or more. When two or more are used at the same time, the total amount thereof is preferably in the above-mentioned range.

＜Other polymerizable compounds＞ The resin composition of the present invention can further contain a polymerizable compound (hereinafter, also referred to as other polymerizable compound) other than the above-mentioned radical polymerizable monomer. Examples of other polymerizable compounds include compounds having hydroxymethyl, alkoxymethyl, or oxymethyl; epoxy compounds; oxetane compounds; and benzophenone compounds.

＜＜Compounds with hydroxymethyl, alkoxymethyl or oxymethyl group＞＞ As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

（式中，t表示1～20的整數，R¹⁰⁴ 表示碳數1～200的t價有機基團，R¹⁰⁵ 表示由-OR¹⁰⁶ 或-OCO-R¹⁰⁷ 表示之基團，R¹⁰⁶ 表示氫原子或碳數1～10的有機基團，R¹⁰⁷ 表示碳數1～10的有機基團。）[化14]

(In the formula, t represents an integer from 1 to 20, R ¹⁰⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , and R ¹⁰⁶ represents a hydrogen atom Or an organic group with 1 to 10 carbons, R ¹⁰⁷ represents an organic group with 1 to 10 carbons.)

（式中，R⁴⁰⁴ 表示碳數1～200的2價有機基團，R⁴⁰⁵ 表示由-OR⁴⁰⁶ 或-OCO-R⁴⁰⁷ 表示之基團，R⁴⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁴⁰⁷ 表示碳數1～10的有機基團。）[化15]

(In the formula, R ⁴⁰⁴ represents a divalent organic group with 1 to 200 carbons, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or an organic group with 1 to 10 carbons. Group, R ⁴⁰⁷ represents an organic group with 1 to 10 carbons.)

（式中，u表示3~8的整數，R⁵⁰⁴ 表示碳數1~200的u價有機基團，R⁵⁰⁵ 表示由-OR⁵⁰⁶ 或、-OCO-R⁵⁰⁷ 表示之基團，R⁵⁰⁶ 表示氫原子或碳數1~10的有機基團，R⁵⁰⁷ 表示碳數1~10的有機基團。）[化16]

(In the formula, u represents an integer from 3 to 8, R ⁵⁰⁴ represents a u-valent organic group with a carbon number of 1 to 200, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and R ⁵⁰⁶ represents hydrogen Atom or an organic group with 1 to 10 carbon atoms, R ⁵⁰⁷ represents an organic group with 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (the above are the trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-t-butylphenol) , 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol) Cresol) and so on.

Also, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML- TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

＜＜Epoxy compound (compound with epoxy group)＞＞ As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy is based on the cross-linking reaction below 200°C, and it is difficult to cause film shrinkage because it does not cause dehydration reaction from cross-linking. Therefore, by containing the epoxy compound, low-temperature hardening and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether and the like Alkylene glycol type epoxy resin; epoxy-containing silicone such as polymethyl (glycidoxypropyl) silicone, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered Trademarks) EXA-4850-150, EPICLONEXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (Trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), etc. Among these, the epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups, so they are preferred.

＜＜Oxetane compound (compound with oxetanyl group)＞＞ Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 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. As a specific example, the ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or in combination. More than species.

＜＜Benzo 㗁𠯤 compound (compound with polybenzo azole group)＞＞ The benzoglyph compound is preferably due to the crosslinking reaction derived from the ring-opening addition reaction, which does not cause outgassing during hardening, thereby reducing thermal shrinkage and suppressing warpage.

Preferable examples of the benzophenone compound include Ba type benzophenone, Bm type benzophenone (manufactured by Shikoku Chemicals Corporation), benzophenone adduct of polyhydroxystyrene resin, and novolac Type dihydrobenzo 㗁𠯤 compound. These can be used alone, or two or more can be mixed.

When other polymerizable compounds are contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to 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 more preferably 30% by mass or less. The other polymerizable compounds may be used alone or in combination of two or more. When two or more are used at the same time, the total amount thereof is preferably in the above-mentioned range.

<Thermal base generator> The resin composition of the present invention preferably contains a thermal base generator. The type of the thermal base generator is not particularly limited, and it contains heat containing at least one selected from the group consisting of acidic compounds that generate bases when heated to 40°C or higher, and ammonium salts with pKa1 of 0-4 and ammonium cations. Alkali generators are preferred. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later. By blending these compounds, the cyclization reaction of polymer precursors and the like can proceed at low temperature. In addition, the thermal alkali generator does not generate alkali unless it is heated. Therefore, even if it coexists with the polymer precursor, the cyclization of the polymer precursor during storage can be suppressed, and the storage stability is excellent.

The thermal base generator preferably contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40°C or higher, an anion having a pKa1 of 0 to 4, and an ammonium salt (A2) of an ammonium cation. The acidic compound (A1) and the ammonium salt (A2) generate alkali when heated. Therefore, the alkali generated from these compounds can promote the cyclization reaction of the polymer precursor, and the polymer precursor can be carried out at low temperature的circulation. In addition, in this specification, the acidic compound refers to the following compound: Take 1 g of the compound into a container, add 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water/tetrahydrofuran=1/4), and stir at room temperature For 1 hour, the solution obtained in this way was measured with a pH (power of hydrogen: pH) meter at 20°C for a compound with a value less than 7 measured.

The alkali generation temperature of the thermal alkali generator used in the present invention is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the alkali generation temperature is preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 165°C or lower. The lower limit of the alkali generation temperature is preferably 130°C or higher, and more preferably 135°C or higher. The alkali production temperature can be measured as follows: For example, using differential scanning calorimetry, heat the compound in a pressure-resistant capsule at 5°C/min to 250°C, read the peak temperature of the heat generation peak with the lowest temperature, and use the peak temperature as the alkali production temperature.

Alkaline secondary amines or tertiary amines produced by hot alkali generators are preferred, and tertiary amines are more preferred. The tertiary amine is highly basic, so it can make the cyclization temperature of the polymer precursor lower. In addition, the boiling point of the alkali produced by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and more preferably 140°C or higher. Furthermore, the molecular weight of the base produced is preferably 80-2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value obtained from the structural formula.

In this embodiment, the acidic compound (A1) preferably contains one or more selected from ammonium salts and compounds represented by formula (101) or (102) described later.

In this embodiment, the above-mentioned ammonium salt (A2)-based acidic compound is preferable. In addition, the above-mentioned ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40°C or higher (preferably 120 to 200°C), or may be a compound other than if heated to 40°C or higher (preferably 120 to 200°C). ～200℃) will produce compounds other than base acidic compounds.

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁷ 表示烴基。式（101）及式（102）中的R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 可以分別鍵結而形成環。In this embodiment, the ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, or may exist outside the molecule of the ammonium cation, but it is preferably present outside the molecule of the ammonium cation. In addition, the presence of an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by covalent bonding. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion. Formula (101) Formula (102) [化17]

In formula (101) and formula (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ^{7 in} formula (101) and formula (102) may be respectively bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-5). [化18]

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ^{7 have} the same meanings as in formula (101) or formula (102). In formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0-5.

In this embodiment, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and the stability of the resin composition can be improved. If pKa1 is 4 or less, the stability of the thermal alkali generator is good, and the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. If pKa1 is 0 or more, the alkali produced is not easily neutralized, and the cyclization efficiency of the polymer precursor is good. The type of anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion, and carboxylate anion is more preferred from the viewpoint of compatibility of salt stability and thermal decomposition. That is, a salt of an ammonium cation and a carboxylate anion is more preferable. The carboxylate anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermal alkali generator that can further improve the stability, curability, and developability of the resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the resin composition can be further improved. In this embodiment, the anion of the carboxylic acid whose pKa1 of the carboxylate anion system is 4 or less is preferable. It is more preferable that pKa1 is 3.5 or less, and it is still more preferable that it is 3.2 or less. According to this aspect, the stability of the resin composition can be further improved. Among them, pKa1 represents the logarithm of the inverse of the dissociation constant of the first proton of the acid, which can be referred to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude , EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software using ACD/pKa (manufactured by ACD/Labs) is used.

式（X1）中，EWG表示拉電子基團。The carboxylate anion is preferably represented by the following formula (X1). [化19]

In formula (X1), EWG represents an electron withdrawing group.

In the present embodiment, the electron withdrawing group means the one whose Hammett substituent constant σm represents a positive value. Among them, σm is explained in detail in Yufu Tono, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents in which σm represents a positive value include CF ₃ groups (σm=0.43), CF ₃ CO groups (σm=0.63), HC≡C groups (σm=0.21), and CH ₂ =CH groups. (σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06) Wait. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式（EWG-1）～（EWG-6）中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [化20]

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

式（XA）中，L¹⁰ 表示選自單鍵或伸烷基、伸烯基、芳香族基、-NR^X -及該等的組合中的2價的連結基，R^X 表示氫原子、烷基、烯基或芳基。In this embodiment, the carboxylate anion is preferably represented by the following formula (XA). Formula (XA) [Chemical 21]

In the formula (XA), L ¹⁰ represents a divalent linking group selected from a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X -and combinations thereof, and R ^X represents a hydrogen atom, an alkane Group, alkenyl or aryl.

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetate anion, and oxalate anion. These can be used preferably.

[化23]

As specific examples of the thermal base generator, the following compounds can be given. [化22]

[化23]

[化24]

The content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above range.

＜Free radical polymerization initiator＞ The resin composition of the present invention preferably contains a radical polymerization initiator. In particular, when a radical polymerizable group is used as a polymer precursor or a radical polymerizable compound is used, it is preferable that the resin composition of the present invention contains a radical polymerization initiator. Examples of the radical polymerization initiator include photo-radical polymerization initiators and thermal radical polymerization initiators. The radical polymerization initiator used in the resin composition of the present invention is preferably a photoradical polymerization initiator.

＜＜Light radical polymerization initiator＞＞ The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that has some effect on the sensitizer excited by light and generates active free radicals. The photo-radical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 mol in the range of about 300-800 nm (preferably 330-500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium compounds such as phosphonium oxides, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron arene complexes, etc. For these details, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and this content is incorporated in this specification. Among the commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acetoxyphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (manufactured by BASF Corporation), which are commercially available products, can be used. As the aminoacetophenone-based initiator, it is also possible to use compounds described in Japanese Patent Application Laid-Open No. 2009-191179 that have an absorption maximum wavelength that matches a light source of wavelengths such as 365 nm or 405 nm. Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (manufactured by BASF Corporation), which are commercially available products, can be used. As a metallocene compound, IRGACURE-784 (made by BASF Corporation) etc. are illustrated.

市售品中，還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製、日本特開2012-014052號公報中記載之光自由基聚合起始劑2）。又，能夠使用TR-PBG-304（Changzhou Tronly New Electronic Materials CO.,LTD.製）、ADEKAARKLS NCI-831及ADEKAARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（DAITO CHEMIX Co.,Ltd.製）。 進而，還能夠使用具有氟原子之肟化合物。作為該等肟化合物的具體例，可舉出日本特開2010-262028號公報中記載之化合物、日本特表2014-500852號公報的0345段中記載之化合物24、36～40、日本特開2013-164471號公報的0101段中記載之化合物（C-3）等。 作為最佳之肟化合物，可舉出日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。As the photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred. As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, and the compounds described in JP 2006-342166 can be used. As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketones, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a radical photopolymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=NOC(=O)- in the molecule. [化25]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Publication 2012-014052 The photo-radical polymerization initiator described in No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 -164471, the compound (C-3) described in paragraph 0101, etc. As the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779 or oximes having sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.

式（I）中，R^I00 係碳數1~20的烷基、藉由一個以上的氧原子而中斷之碳數2~20的烷基、碳數1~12的烷氧基、苯基、碳數1~20的烷基、碳數1~12的烷氧基、鹵素原子、環戊基、環己基、碳數2~12的烯基藉由因一個以上的氧原子而中斷之碳數2~18的烷基及碳數1~4的烷基中的至少一個取代之苯基或聯苯基，R^I01 係由式（II）表示之基團，或者係與R^I00 相同的基團，R^I02 ~R^I04 各自獨立地為碳數1~12的烷基、碳數1~12的烷氧基或鹵素。 [化27]

式中，R^I05 ～R^I07 與上述式（I）的R^I02 ～R^I04 相同。From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl triketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds in the group. More preferable photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium Salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one of the compounds is further preferred, it is even more preferred to use a metallocene compound or an oxime compound, and the oxime compound is even more preferred. In addition, the photoradical polymerization initiator can also use benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-porolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1, alkylanthraquinones, etc. are condensed with aromatic rings Quinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. In addition, a compound represented by the following formula (I) can also be used. [化26]

In formula (I), R ^I00 is an alkyl group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons interrupted by more than one oxygen atom, an alkoxy group with 1 to 12 carbons, a phenyl group, Alkyl groups with 1 to 20 carbons, alkoxy groups with 1 to 12 carbons, halogen atoms, cyclopentyl, cyclohexyl, and alkenyl groups with 2 to 12 carbons. The number of carbons interrupted by one or more oxygen atoms A phenyl or biphenyl substituted with at least one of the ^2-18 alkyl group and the C1-C4 alkyl group, R ^I01 is a group represented by formula (II), or the same group as R ^I00 , R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen. [化27]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^{I04 in the} above formula (I).

In addition, the photoradical polymerization initiator can also use the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photoradical polymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15 % By mass, more preferably 1.0-10% by mass. The thermal radical polymerization initiator may contain only one kind or two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount is preferably in the above range.

＜＜Initiator for thermal radical polymerization＞＞ The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the cyclization of the polymer precursor can be carried out, and the polymerization reaction of the polymer precursor can be carried out, so that a higher degree of heat resistance can be achieved. As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A can be cited.

When a thermal radical polymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5-15 quality%. The thermal radical polymerization initiator may contain only one kind or two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount is preferably in the above range.

＜Solvent＞ The resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines. As esters, for example, preferred ones include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, Alkoxy ethyl acetate, alkoxy butyl acetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Etc.)), 3-alkoxy propionic acid alkyl esters (e.g., 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g., 3-methoxy propionate methyl ester , 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.)), 2-alkoxy propionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate)), 2-alkoxy-2-methyl propionate methyl and 2- Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, preferred ones 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropylene Ether acetate etc. As the ketones, for example, preferable ones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like. As aromatic hydrocarbons, for example, preferable ones include toluene, xylene, anisole, limonene and the like. As the sulfenite, for example, a preferable one includes dimethyl sulfenite. As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide and so on.

Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., a form in which two or more types are mixed is also preferable. In the present invention, it is 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 One solvent or a mixed solvent composed of two or more of acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use both dimethyl sulfoxide and γ-butyrolactone.

Regarding the content of the solvent, from the viewpoint of coating properties, the total solid content of the resin composition of the present invention is preferably 5 to 80% by mass, and more preferably 5 to 75% by mass. Preferably, it is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. The content of the solvent can be adjusted according to the desired thickness and coating method. The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them is preferably in the above range.

＜Migration inhibitor＞ The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the transfer of metal ions originating from the metal layer (metal wiring) into the resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetra Azole ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperazine ring, ormoline ring, 2H-pyran ring and 6H-pyran ring, three pyran ring) compounds, with Thiourea and sulfhydryl compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

In addition, ion scavengers that trap anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701, the compound described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011-059656 can be used. The compound described in paragraph 0052 of JP-A-2012-194520, the compound described in paragraphs 0114, 0116, and paragraph 0118 of JP 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, and the like.

As specific examples of migration inhibitors, the following compounds can be given. [化28]

When the resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and more preferably 0.1 to 1.0% by mass. good. There may be only one type of migration inhibitor, or two or more types. When two or more types of migration inhibitors are used, the total amount is preferably in the above range.

<Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tertiary butylcatechol, 1 ,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl -6-tertiary butyl phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothionine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquine Phenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N- Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. In addition, the following compounds (Me is a methyl group) can also be used. [化29]

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01-5 mass%, more preferably 0.02-3 mass%, and 0.05- 2.5% by mass is more preferable. There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum total is the above range.

＜Metal adhesion improver＞ The resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion with metal materials used for electrodes, wiring, and the like. As a metal adhesion improver, a silane coupling agent etc. are mentioned.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264, International Publication No. The compound described in paragraph 0055 of No. 2014/097594. In addition, 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. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group. [化30]

In addition, the metal adhesion improver can also use the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the sulfide compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer precursor, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass. By setting it as the above-mentioned lower limit or more, the adhesiveness of the cured film after a hardening process and a metal layer becomes good, and by setting it as below the said upper limit, the heat resistance and mechanical properties of the cured film after a hardening process become good. There may be only one type of metal adhesion improver, or two or more types. When two or more are used, it is preferable that the sum total is the above-mentioned range.

＜Other additives＞ The resin composition of the present invention can add various additives such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic Particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

＜＜Thermal acid generator＞＞ The resin composition of the present invention may contain a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more relative to 100 parts by mass of the polymer precursor, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, and therefore the mechanical properties and chemical resistance of the cured film can be further improved. Also, from the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. Only one type of thermal acid generator may be used, or two or more types may be used. When two or more are used, the total amount is preferably in the above range.

＜＜Sensitizing pigment＞＞ The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator undergo chemical changes to decompose and generate free radicals, acids or bases. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, which is incorporated into this specification.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the resin composition of the present invention is preferably 0.01-20% by mass, more preferably 0.1-15% by mass, and 0.5- 10% by mass is more preferable. The sensitizing dye may be used singly, or two or more may be used at the same time.

＜＜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 pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or after oxidation, free radicals can be generated by deprotonation. In particular, thiol compounds can be preferably used. In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention, and more preferably 1-10 parts by mass , 1 to 5 parts by mass is more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total range thereof is preferably the above range.

<<Surfactant>> From the viewpoint of further improving coating properties, various surfactants can be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. [化31]

In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

When the resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the resin composition of the present invention, and more preferably 0.005 to 1.0% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total range is preferably the above range.

＜＜Higher fatty acid derivatives＞＞ In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention, which locally exist in the composition during the drying process after coating. s surface. In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219. 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% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

＜Regarding restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), preferably less than 1 mass ppm, and less than 0.5 mass ppm is furthermore. good. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range. In addition, as a method of reducing the metal impurities accidentally included in the resin composition of the present invention, it is possible to exemplify the selection of a raw material with less metal content as the raw material constituting the resin composition of the present invention. The raw materials are filtered by a filter, and the device is lined with polytetrafluoroethylene to distill under the conditions of suppressing pollution as much as possible.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm Further better. Among them, less than 5 mass ppm is preferred when the halide ion is present, less than 1 mass ppm is more preferred, and less than 0.5 mass ppm is more preferred. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion be in the above-mentioned ranges.

As the storage container of the resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, it is preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins or a bottle in which 6 kinds of resins are formed into a 7-layer structure for the purpose of suppressing the mixing of impurities into the raw materials or compositions. As such a container, for example, the container described in JP 2015-123351 A can be cited.

[Preparation of resin composition] The resin composition of the present invention can be prepared by mixing the aforementioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. In addition, for the purpose of removing foreign substances such as garbage or particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is 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. The filter can be cleaned in advance with an organic solvent. In the filtration step of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. Furthermore, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbents. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

[Cured film] Next, the cured film of the present invention will be described. The cured film of the present invention is obtained from the resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more, for example. Moreover, as an upper limit, it can be 100 micrometers or less, and it can also be 30 micrometers or less. The film thickness of the cured film of the present invention is preferably 1 to 30 μm.

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. The laminated system having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. These metal layers can be preferably used as metal wiring such as rewiring layers.

Examples of the fields to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, a sealing film, a substrate material (base film or cover layer of a flexible printed circuit board, and an interlayer insulating film), or a case where an insulating film for actual mounting use as described above is patterned by etching, and the like can be mentioned. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaki/Supervisor, CMC Technical Library "Polyimide Materials "Basics and Development of Polyimide" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, the use of molded parts, and the production of protective paints and dielectric layers in electronics, especially microelectronics. [Example]

Hereinafter, the present invention will be described in further detail with examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

<Examples and Comparative Examples> The components described in the following table were mixed to obtain a resin composition.

[Table 1] Polymer precursor Initiator Polymerizable monomer Solvent Thermal alkali generator Silane coupling agent Polymerization inhibitor Migration inhibitor species Mixing amount (parts by mass) species Mixing amount (parts by mass) species Mixing amount (parts by mass) species Mixing amount (parts by mass) species Mixing amount (parts by mass) species Mixing amount (parts by mass) species Mixing amount (parts by mass) species Mixing amount (parts by mass) Example 1 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 2 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 3 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 4 A-2 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 5 A-1 37 B-2 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 6 A-1 37 B-3 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 7 A-1 37 B-4 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 8 A-1 37 B-1 1.5 C-2 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 9 A-1 37 B-1 1.5 C-3 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 10 A-1 37 B-1 1.5 C-4 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 11 A-1 37 B-1 1.5 C-1 6 D-3 D-4 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 12 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-2 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 13 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-3 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 14 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-2 1 G-1 0.1 H-1 0.1 Example 15 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-3 0.3 F-3 1 G-1 0.1 H-1 0.1 Example 16 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-2 0.1 H-1 0.1 Example 17 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-2 0.1 Example 18 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 19 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 20 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-2 0.4 Example 21 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-4 0.3 F-1 1 G-1 0.1 H-1 0.1 Example 22 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-4 0.3 F-3 1 G-1 0.1 H-1 0.1 Comparative example 1 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1 Comparative example 2 A-1 37 B-1 1.5 C-1 6 D-1 D-2 44 11 E-1 0.3 F-1 1 G-1 0.1 H-1 0.1

A-2：下述結構的聚苯并㗁唑前驅物（Mw=25000） [化33]

The raw materials listed in the above table are as follows. (Polymer precursor) A-1: Polyimide precursor with the following structure (Mw=25000) [Chem. 32]

A-2: Polybenzoxazole precursor with the following structure (Mw=25000) [Chemical 33]

(Initiator) B-1: IRGACURE OXE 01 (made by BASF) B-2: IRGACURE OXE 02 (made by BASF Corporation) B-3: IRGACURE 784 (made by BASF) B-4: NCI-831 (manufactured by ADEKA CORPORATION)

(Polymerizable monomer) C-1: SR-209 (manufactured by Arkema) C-2: M-306 (manufactured by TOAGOSEI CO., LTD.) C-3: A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd.) C-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Solvent) D-1: N-Methylpyrrolidone D-2: Ethyl lactate D-3: γ-butyrolactone D-4: Dimethyl sulfide

(Thermal base generator) E-1: The following compound E-2: The following compound E-3: The following compound E-4: The following compound [Chemical Formula 34]

(Silane coupling agent) F-1: The following compound (In the following formula, Et represents an ethyl group.) F-2: The following compound (In the following formula, Et represents an ethyl group.) F-3: The following compound (hereinafter In the formula, Et represents an ethyl group.) [化35]

(Polymerization inhibitor) G-1: 1,4-Benzoquinone G-2: 4-Methoxyphenol

(Migration inhibitor) H-1: 1,2,4-triazole H-2: 1H-tetrazole

＜Evaluation＞ ＜＜Evaluation of mechanical properties＞＞ On a silicon wafer with a copper metal layer formed on the surface, the resin composition is spin-coated until the cured film thickness becomes about 10 μm. After drying, it is heated in a temperature programmed curing furnace (VF-2000 type, KOYO THERMO SYSTEMS CO. , LTD.), the atmosphere in the furnace was adjusted to the conditions described in the following table, and heating was performed under the conditions described in the following table, thereby obtaining a cured film. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were replaced with nitrogen and adjusted with an oxygen concentration meter (manufactured by Yokogawa Electric Corporation). Using a dicing machine (Model DAD3350, manufactured by DISCO Corporation), the obtained cured film was cut into short strips with a width of 3 mm, and then peeled from the silicon wafer with 46% hydrofluoric acid. The ductility of the cured film peeled from the silicon wafer was measured, and the mechanical properties were evaluated using the following criteria. The ductility of the cured film was measured with a tensile testing machine (UTM-II-20 type, manufactured by ORIENTEC Co., LTD) in accordance with ASTM D882-09. A: The ductility is more than 60% B: Ductility is 50% or more and less than 60% C: Ductility is 40 or more and less than 50% D: Ductility is less than 40%

＜Copper Corrosion＞ On the copper substrate, the resin composition is spin-coated until the cured film thickness becomes about 10 μm. After drying, the furnace is heated in a temperature programmed curing furnace (Model VF-2000, manufactured by KOYO THERMO SYSTEMS CO., LTD.) The atmosphere inside was adjusted to the conditions described in the following table, and heating was performed under the conditions described in the following table, thereby obtaining a cured film. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were replaced with nitrogen and adjusted with an oxygen concentration meter (manufactured by Yokogawa Electric Corporation). After cutting the obtained cured film into short strips with a width of 3 mm with a cutting machine (Model DAD3350, manufactured by DISCO Corporation), it was peeled from the copper substrate with an aqueous ferric chloride solution. The copper substrate after peeling the cured film formed on the surface was taken as the copper substrate 1. Regarding the copper substrate (bare substrate) before the hardened film is formed and the copper substrate after peeling off the hardened film formed on the surface (copper substrate 1), surface observation (discoloration/corrosion confirmation) with an optical microscope (manufactured by NIKON CORPORATION) and Cross-sectional observation (confirmation of film thickness variation/concavity and convexity) with a scanning electron microscope (manufactured by Hitachi, Ltd.), and the copper corrosion resistance was evaluated according to the following criteria. A: The copper substrate 1 has no discoloration/corrosion, film thickness fluctuation, or unevenness, and has the same properties as the bare substrate. B: Compared with the bare substrate, the copper substrate 1 has a slightly darker purple color, but there is no film thickness fluctuation or unevenness. C: Compared with the bare substrate, the copper substrate 1 has a slightly thicker purple color, and the copper is slightly damaged and becomes slightly uneven. D: Compared with the bare substrate, the copper substrate 1 has a darker purple color, and the copper is damaged and severely uneven.

[Table 2] Furnace atmosphere Heating conditions (temperature/time) Mechanical properties Copper corrosion Oxygen partial pressure (Pa) Atmosphere pressure (MPa) Oxygen concentration (volume ppm) Example 1 6 0.1 60 170℃/2 hours B A Example 2 150 0.1 1500 170℃/2 hours B C Example 3 50 0.1 500 170℃/2 hours A A Example 4 50 0.1 500 170℃/2 hours A A Example 5 50 0.1 500 170℃/2 hours A A Example 6 50 0.1 500 170℃/2 hours A A Example 7 50 0.1 500 170℃/2 hours B A Example 8 50 0.1 500 170℃/2 hours B A Example 9 50 0.1 500 170℃/2 hours B A Example 10 50 0.1 500 170℃/2 hours B A Example 11 50 0.1 500 170℃/2 hours A A Example 12 50 0.1 500 170℃/2 hours B A Example 13 50 0.1 500 170℃/2 hours A A Example 14 50 0.1 500 170℃/2 hours A A Example 15 50 0.1 500 170℃/2 hours A A Example 16 50 0.1 500 170℃/2 hours A A Example 17 50 0.1 500 170℃/2 hours A A Example 18 50 0.1 500 230℃/3 hours A B Example 19 50 0.1 500 350℃/1 hour A A Example 20 50 0.1 500 170℃/2 hours A A Example 21 50 0.1 500 170℃/2 hours A A Example 22 50 0.1 500 170℃/2 hours A A Comparative example 1 1 0.1 10 170℃/2 hours D A Comparative example 2 200 0.1 2000 170℃/2 hours C D

As shown in the above table, the examples can form a cured film with excellent mechanical properties.

Claims (10)

A method for manufacturing a hardened film, which includes: Applying a resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoazole precursor and a radical polymerizable monomer to the substrate to form a film; as well as A step of heating and curing the film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa. The method of manufacturing a cured film according to claim 1, wherein The atmospheric pressure in the heating and hardening step is 0.08 to 0.12 MPa. The method of manufacturing a cured film according to claim 1 or 2, wherein In the heat curing step, the film is heated to 170-350°C. The method of manufacturing a cured film according to claim 1 or 2, wherein Between the step of forming the film and the step of heating and curing, a step of exposing the film and a step of developing the exposed film are included. The method of manufacturing a cured film according to claim 1 or 2, wherein The substrate to which the resin composition is applied is a metal substrate or a substrate containing a metal layer. The method of manufacturing a cured film according to claim 1 or 2, which is a method of manufacturing a cured film for an insulating layer. A resin composition comprising at least one polymer precursor and a radical polymerizable monomer selected from the group consisting of polyimide precursors and polybenzoxazole precursors, This resin composition is used in the method for producing a cured film as described in claim 1 or 2. A cured film obtained from the resin composition described in claim 7. A method for manufacturing a laminate, which includes a step of forming a cured film by the method for manufacturing a cured film according to any one of claims 1 to 6 and a step of forming a metal layer on the surface of the cured film. A method for manufacturing a semiconductor element, which includes the method for manufacturing a cured film according to any one of claims 1 to 6.