KR20210057104A - Cured film manufacturing method, resin composition, cured film, laminate manufacturing method, and semiconductor device manufacturing method - Google Patents

Abstract

A process of forming a film by applying a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radically polymerizable monomer to a substrate, and an oxygen partial pressure of 6 to 150 Pa. A method for producing a cured film including a step of heating and curing in a phosphorus atmosphere. A resin composition, a cured film, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device.

Description

Cured film manufacturing method, resin composition, cured film, laminate manufacturing method, and semiconductor device manufacturing method

The present invention relates to a method for producing a cured film using a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer. Moreover, the present invention relates to a method for manufacturing a resin composition, a cured film, a laminate, and a method for manufacturing a semiconductor device.

Since cyclized and cured resins such as polyimide resin and polybenzoxazole resin are excellent in heat resistance and insulation, they are applied to various uses. Although the use thereof is not particularly limited, for example, a semiconductor device for mounting may be used as an insulating film or a sealing material, or as a protective film. In addition, it is also used as a base film or a coverlay for a flexible substrate.

In general, such a polyimide resin has low solubility in a solvent. Therefore, a method of dissolving in a solvent in the form of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor, is often used. Thereby, excellent handling property can be realized, and when manufacturing each product as described above, it can be applied and processed in various forms on a substrate or the like. Thereafter, the polymer precursor can be heated to cyclize and form a cured product. In addition, when the polymer precursor is heated to cyclize, in order to prevent oxidation of the substrate or the like, heating is performed in an atmosphere in which the oxygen concentration is reduced, such as under a nitrogen atmosphere.

For example, Patent Document 1 describes forming a photosensitive polyimide resin layer by heating a photosensitive polyimide precursor layer at 200°C or more and 350°C or less in an environment in which the oxygen concentration is 50 ppm or less. 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 again in an atmosphere containing oxygen.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-054451 Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-031564

In producing a cured film using a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor, it is desired to further lower the heating curing temperature. However, as the heat curing temperature is lowered, mechanical properties such as elongation of the resulting cured film tend to decrease. Also in the inventions described in Patent Documents 1 and 2, it was difficult to produce a cured film that satisfies the level required in recent years.

Accordingly, an object of the present invention is to provide a method for producing a cured film having excellent mechanical properties, a method for producing a resin composition, a cured film, a laminate, and a method for producing a semiconductor device.

According to the study of the present inventors, a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer was used as the resin composition, and the resin composition was prepared. It has been found that a cured film excellent in mechanical properties can be obtained by heat-curing the film obtained by using it in an atmosphere in which the partial pressure of oxygen is 6 to 150 Pa, and the present invention has been completed. The present invention provides the following.

<1> a step of forming a film by applying a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radically polymerizable monomer to a substrate,

A method for producing a cured film comprising a step of heat-curing the film in an atmosphere in which the partial pressure of oxygen is 6 to 150 Pa.

<2> The production method of the cured film according to <1>, wherein the atmospheric pressure in the step of heating and curing is 0.08 to 0.12 MPa.

<3> The process of heat-hardening is the manufacturing method of the cured film as described in <1> or <2> which heats a film to 170-350 degreeC.

The method for producing a cured film according to any one of <1> to <3>, including a step of exposing a film and a step of developing a film after exposure between the step of forming a <4> film and the step of heat curing.

The method for producing a cured film according to any one of <1> to <4>, wherein the substrate to which the <5> resin composition is applied is a metal substrate or a substrate including a metal layer.

The method for producing a cured film according to any one of <1> to <5>, which is a method for producing a cured film for <6> insulating layers.

<7> A resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a radically polymerizable monomer,

A resin composition used in the method for producing a cured film according to any one of <1> to <6>.

<8> A cured film obtained from the resin composition according to <7>.

<9> A method for producing a laminate, including a step of forming a cured film by the method for producing 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> The manufacturing method of a semiconductor device including the manufacturing method of a cured film in any one of <1>-<6>, or the manufacturing method of a laminated body as described in <9>.

According to the present invention, a method for producing a cured film having excellent mechanical properties, a method for producing a resin composition, a cured film, a laminate, and a method for producing a semiconductor device can be provided.

Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "~" is used for the meaning including the numerical value described before and behind it as a lower limit and an upper limit.

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the notation of the group (atomic group) in the present specification, the notation that does not describe substitution or unsubstituted includes not only having no substituent but also having a substituent. For example, the "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams in exposure unless otherwise specified. In addition, as the light used for exposure, in general, a bright ray spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, actinic rays such as electron rays, or radiation can be mentioned.

In the present specification, "(meth)acrylate" represents both or any one of "acrylate" and "methacrylate", and "(meth)acrylic" refers to "acrylic" and "methacryl". It represents both or either, and "(meth)acryloyl" represents both or any one of "acryloyl" and "methacryloyl".

In the present specification, the term "step" is included in the term as long as the desired action of the step is achieved, not only in an independent step, but also in a case where it is not clearly distinguishable from other steps.

The physical property value in the present invention is a value under a temperature of 23°C and an atmospheric pressure of 101325 Pa, unless otherwise specified.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement), unless otherwise specified, and are defined as polystyrene conversion values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard column HZ-L, TSKgel Super HZM-M as columns , TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In this measurement, THF (tetrahydrofuran) is used as the eluent unless otherwise specified. In addition, the detection is assumed to use a UV ray (ultraviolet) wavelength 254 nm detector unless otherwise specified.

The temperature in the present invention is 23°C unless otherwise specified.

[Method of manufacturing cured film]

The method for producing a cured film of the present invention is a step of forming a film by applying a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer to a substrate. It is characterized by including a (film formation process) and a process (heat curing process) of heat-curing the film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa.

According to the present invention, a cured film excellent in mechanical properties such as elongation can be formed. The detailed reason is unclear, but by performing heat curing of the film in an atmosphere of the predetermined oxygen partial pressure, the amount of oxygen present is increased, thereby slightly lowering the crosslinking density of the original radically polymerizable monomer and the polymer precursor, and the interaction between the polymer precursors. This is alleviated and it is assumed that this was achieved by increasing the resistance in the stress direction. In addition, it is generally considered that the polymerization reaction of the radical polymerizable monomer is easily inhibited in the presence of oxygen. For this reason, when heat-curing a film obtained by using a resin composition containing a radical polymerizable monomer, a lower oxygen partial pressure during heat curing is considered to yield a cured film having superior mechanical properties such as elongation, but heat curing of the film. It is surprising that the mechanical properties such as elongation of the resulting cured film were improved by performing in an atmosphere of an oxygen partial pressure within the above range.

Further, since the oxygen partial pressure during heat curing is within the above range, oxidation of the substrate and the like can also be suppressed. For this reason, it is particularly effective in the case of using a metal layer or a metal substrate as the substrate.

It is preferable that the method for producing a film of the present invention includes a step of exposing the film and a step of developing the film after exposure 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 production method of the film of the present invention includes the following steps (a) to (d). According to this aspect, a pattern of a cured film excellent in mechanical properties such as elongation can be formed. The cured film formed in this way can be preferably used as an insulating layer. In particular, it can be preferably used as an interlayer insulating film for redistribution layers.

(a) a step of forming a film by applying a resin composition to a substrate (film forming step),

(b) After the film formation step, the step of exposing the film (exposure step),

(c) the process of developing the film after exposure (development process),

(d) The step of heat-curing the developed film in an atmosphere in which the partial pressure of oxygen is 6 to 150 Pa (heat curing step).

Hereinafter, each process will be described in detail.

<Film formation process>

In the film forming step, a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer is applied to a substrate to form a film. Details of the resin composition will be described later.

The type of the substrate can be appropriately determined according to the application. For example, an inorganic substrate, a resin substrate, and a resin composite material substrate may be mentioned. Examples of the inorganic substrate include a silicon substrate, a silicon nitride substrate, a polysilicon substrate, a silicon oxide substrate, an amorphous silicon substrate, a glass substrate, a quartz substrate, and a metal substrate. A metal layer such as molybdenum, titanium, aluminum, or copper may be formed on the surfaces 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. As a resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyldiglycol carbonate, polyamide , Polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluorine resin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, And a substrate made of a synthetic resin such as a silicone resin, an ionomer resin, a cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide, an olefin, a cellulose, or an episulfide compound. 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, a cured film having excellent mechanical properties such as elongation can be formed while suppressing oxidation of the metal, which is particularly effective when such a substrate is used.

As a means for applying the resin composition to the substrate, application is preferable. Specifically, as a means to be applied, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and The ink jet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the formed film (resin composition layer), more preferably a spin coating method, a slit coating method, a spray coating method, or an inkjet method. A film (resin composition layer) having a desired thickness can be obtained by adjusting an appropriate solid content concentration or application condition according to the method. In addition, a coating method can be appropriately selected depending on the shape of the substrate, and if it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and if a rectangular substrate is a slit coating method, a spray coating method, an inkjet method And the like are preferred. In the case of the spin coating method, it can be applied under conditions of about 10 seconds to 1 minute at a rotation speed of, for example, 500 to 2000 rpm.

In the film forming step, after applying the resin composition to the substrate, drying may be performed in order to remove the solvent. The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, and still more preferably 90 to 110°C. As for the drying time, 30 seconds-20 minutes are illustrated, 1-10 minutes are preferable, and 3-7 minutes are more preferable.

<Exposure process>

The method for producing a film of the present invention may include a step of exposing the film (exposure step) after the film forming step. In the exposure step, the film (resin composition layer) can be exposed in a pattern by exposing the film (resin composition layer) through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like.

The exposure amount is not specifically determined as long as the film (resin composition layer) can be cured, for example, in terms of exposure energy at a wavelength of 365 nm, ^{it is preferable to irradiate 100 to 10000 mJ/cm 2} , and 200 to 8000 mJ/cm ² irradiation It is more preferable to do it. The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and 240 to 550 nm is preferable. The exposure wavelength is, in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g line (wavelength 436nm), h Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (Wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, etc. are mentioned. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. In this way, a particularly high exposure sensitivity can be obtained.

<Development process>

The method for producing a film of the present invention may include a step (development step) of developing a film (resin composition layer) after exposure. By performing development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as puddle, spray, immersion, or ultrasonic waves can be employed.

Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. It is preferable that the developing solution contains an organic solvent, and it is more preferable that the developing solution 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 containing an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula with ChemBioDraw.

Organic solvents are esters, for example, ethyl acetate, acetic acid-n-butyl, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionate methyl, 3-alkyloxypropionate ethyl, etc.) For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g. 2-alkyloxy Methyl propionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxyethylpropionate)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2-methylpropionate ethyl (e.g. 2-methoxy-2-methylpropionate methyl, 2-ethoxy Ethyl -2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, di Ethylene 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 ketones, such as methyl ethyl ketone, cyclohexanone, As clopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons, such as toluene, xylene, anisole, limonene, etc., as sulfoxides And dimethyl sulfoxide are suitably mentioned.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

As for the developer, it is preferable that 50 mass% or more is an organic solvent, it is more preferable that 70 mass% or more is an organic solvent, and it is still more preferable that 90 mass% or more is an organic solvent. Moreover, 100 mass% of a developer may be an organic solvent.

As the developing time, 10 seconds to 5 minutes are preferable. The temperature of the developer at the time of development is not particularly determined, but can usually be performed at 20 to 40°C.

After treatment with a developer, you may further rinse. It is preferable to perform rinsing with a solvent different from the developer. For example, it can rinse using a solvent contained in a resin composition. The rinse time is preferably 5 seconds to 1 minute.

<heat curing process>

In the heat curing step, the film (in the case of including the exposure step and the developing step, the developed film) 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, for example, a heating chamber.

In the present invention, the film is heated in an atmosphere in which the partial pressure of oxygen is 6 to 150 Pa. The upper limit of the oxygen partial pressure in the heating step is preferably 120 Pa or less, more preferably 100 Pa or less, and still more preferably 60 Pa or less from the reason of suppressing corrosion of the substrate. In addition, the lower limit of the oxygen partial pressure is preferably 7 Pa or more, more preferably 10 Pa or more, and still more preferably 30 Pa or more, because a cured film having mechanical properties such as more excellent elongation is easily obtained. In addition, in the case of heating the film in the heating chamber, the partial pressure of oxygen in the heating chamber corresponds to the partial pressure of oxygen in the atmosphere of the heating and curing step.

As a method of adjusting the oxygen partial pressure in the atmosphere of the heating and curing process to the above range, a method of adjusting the partial pressure of oxygen by replacing the gas in the atmosphere in the heating chamber with an inert gas, a method of adjusting the partial pressure of oxygen by depressurizing the inside of the heating chamber, etc. For example, a method of adjusting the partial pressure of oxygen by replacing the gas in the atmosphere in the heating chamber with an inert gas is preferable from the reason of the stability of the film. Examples of the inert gas include nitrogen, helium, and argon.

The atmospheric pressure in the heat-curing step is preferably from 0.08 to 0.12 MPa, and more preferably from 0.09 to 0.11 MPa, from the reason of the stability of the film. In addition, in the case of heating the film in the heating chamber, the pressure in the heating chamber corresponds to the atmospheric pressure in the heating and curing step.

Moreover, it is also preferable that the oxygen concentration in the atmosphere of the heat curing step is more than 60 ppm by volume and not more than 1500 ppm by volume. The lower limit is preferably 65 ppm by volume or more, more preferably 100 ppm by volume or more, and still more preferably 500 ppm by volume or more. The upper limit is preferably 1400 ppm by volume or less, more preferably 1200 ppm by volume or less, and still more preferably 1000 ppm by volume or less. In addition, in the case of heating the film in the heating chamber, the oxygen concentration in the heating chamber corresponds to the oxygen concentration in the atmosphere of the heating and curing step.

The heating temperature (maximum heating temperature) of the film in the heat curing step is preferably 50°C or higher, more preferably 80°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, and 160°C or higher. It is more preferable that it is, and it is still more preferable that it is 170 degreeC or more. As the upper limit, it is preferably 500°C or less, more preferably 450°C or less, more preferably 350°C or less, even more preferably 250°C or less, and even more preferably 220°C or less. Moreover, it is preferable that the heating temperature (maximum heating temperature) of the film is 170 to 350°C.

Heating is preferably performed from the temperature at the beginning of heating to the highest heating temperature at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the temperature rising rate to 1° C./min or more, excessive volatilization of amines can be prevented while ensuring productivity, and by setting the temperature rising 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 from 20°C to 150°C, more preferably from 20°C to 130°C, and still more preferably from 25°C to 120°C. The temperature at the start of heating refers to the temperature at the time of starting the step of heating to the maximum heating temperature. For example, when drying after applying a resin composition on a substrate, this is the temperature of the film (layer) after drying, and for example, the temperature is gradually increased from 30 to 200°C lower than the boiling point of the solvent contained in the resin composition. It is desirable.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and still more preferably 30 to 240 minutes.

In particular, in the case of forming a multilayer laminate, from the viewpoint of adhesion between the layers of the cured film, it is preferable to heat the film at 180°C to 320°C, and more preferably at 180°C to 260°C. The reason is unclear, but it is thought that by setting it as this temperature, the crosslinking reaction between the ethyneyl groups of the polymer precursor between layers progresses.

Heating may be performed in stages. For example, a pretreatment process such as raising the temperature from 25℃ to 180℃ at 3℃/min, maintaining at 180℃ for 60 minutes, raising the temperature from 180℃ to 200℃ at 2℃/min, and maintaining at 200℃ for 120 minutes You may do it. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and still more preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in US Patent Publication No. 9159547. It is possible to improve the properties of the film by such a pretreatment process. The pretreatment step may be performed in a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, 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.

Moreover, you may cool after heating, and it is preferable that it is 1-5 degreeC/min as a cooling rate in this case.

Through the above process, a cured film can be manufactured. As an applicable field of the cured film, an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc. are mentioned. In addition, a sealing film, a substrate material (a base film or a coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above is patterned by etching. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervision, CMC Technical Library "Basic and Development of Polyimide Materials" published in November 2011, Japan Polyimide-Aromatic Polymer Research Society/Edition "Latest Polyimide Basics and Applications" N·T·S, August 2010, etc. can be referred. In addition, the cured film can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, use for etching of molded parts, and the production of protective lacquers and dielectric layers in electronics, particularly microelectronics.

[Method of manufacturing laminate]

The manufacturing method of the laminate of the present invention includes a step of forming a cured film (cured film forming step) and a step of forming a metal layer on the surface of the cured film (metal layer forming step) by the method for producing a cured film of the present invention described above. Includes.

As the type of the metal layer formed on the surface of the cured film, without particular limitation, existing metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper and aluminum are more It is preferred, and copper is more preferred. The method of forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination thereof are contemplated. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating may be mentioned. The thickness of the metal layer is preferably 0.1 to 50 µm, and more preferably 1 to 10 µm in the thickest portion.

In the method for producing a laminate of the present invention, it is also preferable to form a cured film on the surface of the cured film (resin layer) or the metal layer again after the metal layer forming step by the method for producing the cured film of the present invention described above.

Moreover, in the manufacturing method of a laminated body of this invention, a cured film formation process and a metal layer formation process may be alternately performed a plurality of times (preferably 2 to 7 times, more preferably 2 to 5 times). By doing in this way, a laminate of a multilayer wiring structure such as a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer in which a plurality of cured films (resin layers) and metal layers are alternately laminated can be produced.

[Method of manufacturing semiconductor device]

The manufacturing method of the semiconductor device of the present invention includes the manufacturing method of the cured film of the present invention described above, or the manufacturing method of the laminate of the present invention described above. As a specific example of the semiconductor device, the description of paragraphs 0213 to 0218 of JP 2016-027357 A and the description of Fig. 1 can be referred to, and these contents are incorporated herein by reference.

[Resin composition]

Next, the resin composition used in the method for producing a film of the present invention will be described.

<Polymer precursor>

The resin composition of the present invention contains a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. The polymer precursor used in the present invention is preferably a polyimide precursor because the effect of the present invention is more easily obtained.

<< polyimide precursor >>

As a polyimide precursor, it is preferable to contain the structural unit represented by following formula (1). By setting it as such a structure, a resin composition excellent in film strength is obtained.

[Formula 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 Represents a monovalent organic group.

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

<<<R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, and a linear or branched aliphatic group having 2 to 20 carbon atoms, and 3 to 20 carbon atoms A group consisting of a branched aliphatic group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

It is preferable that R ¹¹¹ is 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, and two or more types may be used.

Specifically, the diamine is preferably a C2-C20 linear aliphatic group, a C3-C20 branched or cyclic aliphatic group, a C6-C20 aromatic group, or a group consisting of a combination thereof. And, it is more preferable that it is a diamine containing a C6-C20 aromatic group. The following is mentioned as an example of an aromatic group.

[Formula 2]

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHCO- and a group selected from a combination thereof is preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, And more preferably a group selected from _{-SO 2 -, -CH 2} -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) _2- It is more preferable that it is a divalent group selected from the group consisting of.

As diamine, specifically 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane ; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane Phosphorus and isophoronediamine; Meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether , 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodi Phenylsulfide, 4,4'- 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)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'- Bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy) Si) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl) -10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5 -Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl Sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethylmethacrylate, 2,4- And 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-tri Methyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane , Diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis (4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2 -Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4 -(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl ]Hexafluoropropane, parabis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4, 4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'- Bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3 ,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2', At least one diamine selected from 5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl Can be lifted.

Moreover, diamines (DA-1) to (DA-18) shown below are also preferable.

[Formula 3]

Moreover, a diamine which has at least 2 or more alkylene glycol units in a main chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of any one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably a diamine not containing an aromatic ring. As a specific example, 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)ethoxy) )Propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like, but are not limited thereto.

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, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

[Formula 4]

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

It is preferable that R ^{111 is represented by -Ar 0} -L ⁰ -Ar ⁰ -from the viewpoint of the flexibility of the resulting cured film. However, Ar ⁰ is each independently an aromatic hydrocarbon group (6 to 22 carbon atoms are preferable, and 6 to 18 are more preferable, and 6 to 10 are particularly preferable), and a phenylene group is preferable. L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO -And a group selected from combinations thereof. A preferable range has the same meaning as A mentioned above.

It is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, it is more preferable that it is a divalent organic group represented by Formula (61) from the viewpoint of i-ray transmittance and availability.

[Formula 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, a methyl group, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. to be.

Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc. I can.

[Formula 6]

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

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

<<<R ¹¹⁵ >>>

^{R 115} in formula (1) represents a tetravalent organic group. As a tetravalent organic group, it is preferable that it is a group containing an aromatic ring, and the group represented by following formula (5) or formula (6) is more preferable.

[Formula 7]

R ¹¹² has the same meaning as A, and the preferred range is also the same.

^{Specific examples of the tetravalent organic group represented by R 115} in formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group has been removed from the tetracarboxylic acid dianhydride. Tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[Formula 8]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ and R ¹¹⁵ are as defined in formula (1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-di Phenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4 '-Diphenylmethanetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3 ,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid 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 Water, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1, 4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) at least 1 selected from ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms Species are illustrated.

Moreover, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as a preferable example.

[Formula 9]

<<<R ¹¹³ and R ¹¹⁴ >>>

^{R 113} and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group. The radical polymerizable group is a group capable of crosslinking reaction by the action of a radical, and preferred examples include 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, and a group represented by the following formula (III).

[Formula 10]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, 1 to 12 carbon atoms are It is preferable, 1-6 are more preferable, 1-3 are especially preferable; As for the number of repetitions, 1-12 are preferable, 1-6 are more preferable, 1-3 are especially preferable). In addition, the (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , A dodecamethylene group, and -CH ₂ CH(OH)CH ₂ -are mentioned, and an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH(OH)CH ₂ -are more preferable.

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, as a ^{monovalent organic group of R 113} or R ¹¹⁴ , having 1, 2 or 3, preferably 1 acid group, an aliphatic group, an aromatic group and an arylalkyl group Etc. are mentioned. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl 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 are mentioned. The acid group is preferably a hydroxyl group. That is, ^{it is preferable that R 113} or R ¹¹⁴ is a group having a hydroxyl group.

As the ^{monovalent organic group represented by R 113} or R ¹¹⁴ , a substituent which improves the solubility of a developer is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, ^{it is preferable that R 113} or R ¹¹⁴ is a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferably included, and an alkyl group substituted with an aromatic group is more preferable.

The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of cyclic). The alkyl group may be linear, branched or cyclic. As a linear or branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, iso A propyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group are mentioned. 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bonyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camporoyl group, dicyclohexyl group and pinenyl group. Can be lifted. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

As an aromatic group, specifically, a substituted or unsubstituted aromatic hydrocarbon group (as a cyclic structure which comprises a group, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring) , An indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (cyclic structure constituting the group Examples include fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolizin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring , A phenanthroline ring, a cyantran ring, a chromane ring, a xanthene ring, a phenoxacyin ring, a phenothiazine ring, or a phenazine ring).

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. There is no upper limit in particular, but 50 mass% or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by formula (1). Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(paraaminophenyl)octamethylpentasiloxane, and the like.

It is preferable that the structural unit represented by Formula (1) is a structural unit represented by Formula (1-A) or (1-B).

[Formula 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, and R ^{At least one of 113} and R ¹¹⁴ is preferably a group containing a radical polymerizable group, and more preferably a radical polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently the same as the preferred range of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ^{114 in} the formula (1) to be.

A preferred range of R is ^112, the same meaning as R ¹¹² in formula (5), among others and more preferably an oxygen atom.

The bonding position of the carbonyl group in the formula to the benzene ring is preferably 4, 5, 3', and 4'in the formula (1-A). In formula (1-B), it is preferable that they are 1, 2, 4, 5.

In a polyimide precursor, although one type may be sufficient as a structural unit represented by Formula (1), it may be two or more types. Moreover, you may contain the structural isomer of a structural unit represented by Formula (1). Moreover, the polyimide precursor may contain other types of structural units in addition to the structural units of the above formula (1).

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of the total constituent units is a polyimide precursor which is a constituent unit represented by formula (1). It is illustrated. As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 500,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-25000, More preferably, it is 2000-500,000, More preferably, it is 4000-25000.

1.5-3.5 are preferable and, as for the dispersion degree of the molecular weight of a polyimide precursor, 2-3 are more preferable.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, a dicarboxylic acid or a dicarboxylic acid derivative is halogenated using a halogenating agent, and then obtained by reacting with a diamine.

In the manufacturing method of a polyimide precursor, it is preferable to use an organic solvent at the time of reaction. One type of organic solvent may be sufficient, and two or more types may be sufficient as it.

As an organic solvent, although it can determine suitably depending on a raw material, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone are illustrated.

At the time of production of the polyimide precursor, it is preferable to include a step of depositing a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and a polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid precipitation can be achieved.

<<Polybenzoxazole precursor>>

It is preferable that the polybenzoxazole precursor contains a structural unit represented by the following formula (2).

[Formula 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. As a divalent organic group, an aliphatic group (carbon number 1-24 is preferable, 1-12 are more preferable, 1-6 are especially preferable), and an aromatic group (carbon number 6-22 is preferable, and 6-14 are more It is preferable, and a group containing at least one of (6-12 is particularly preferable) is preferable. Examples of the aromatic group constituting R ^{121 include R 111 in} the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it has the ^{same meaning as R 115} in said formula (1), and a preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

Each of R ¹²³ and R ¹²⁴ independently represents a hydrogen atom or a monovalent organic group, has the ^{same meaning as R 113} and R ¹¹⁴ in the formula (1), and the preferred range is also the same.

The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2).

From the viewpoint of being able to suppress the occurrence of warpage of the cured film due to ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit.

[Formula 13]

Z has a structure a and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is a carbon number 1 It is a hydrocarbon group of ~ 10 (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and ^{at least one of R 3s} , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to carbon atoms). 22, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms, and the remainder is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, particularly It is preferably an organic group having 1 to 6) carbon atoms, and each may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z portion, preferably, 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), preferable Z is that R ^5s and R ^6s in the b structure are a phenyl group. Moreover, it is preferable that it is 400-4,000, and, as for the molecular weight of a structure represented by Formula (SL), 500-3,000 are more preferable. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus after dehydration and cyclization of the polybenzoxazole precursor is lowered, so that both the effect of suppressing warpage and the effect of improving solubility can be achieved.

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the tetracarboxylic dianhydride is a structural unit in terms of improving alkali solubility. It is preferable to further include as. As an example of such a tetracarboxylic acid residue, the example of R ¹¹⁵ in Formula (1) is mentioned.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 500,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-25000, More preferably, it is 2000-500,000, More preferably, it is 4000-25000.

1.5-3.5 are preferable and, as for the dispersion degree of the molecular weight of a polybenzoxazole precursor, 2-3 are more preferable.

In the resin composition of the present invention, the content of the polymer precursor is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and 50% by mass based on the total solid content of the resin composition. It is still more preferable that it is% or more, it is still more preferable that it is 60 mass% or more, and it is still more preferable that it is 70 mass% or more. In addition, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, based on the total solid content of the resin composition. It is still more preferable that it is 95 mass% or less.

The resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<radical polymerizable monomer>

The resin composition of the present invention contains a radically 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 ethylenically unsaturated bonds such as vinyl group, allyl group, vinylphenyl group, and (meth)acryloyl group. The radical polymerizable group is preferably a (meth)acryloyl group.

The number of radical polymerizable groups that the radical polymerizable monomer has may be one or two or more, but the radical polymerizable compound preferably has two or more radical polymerizable groups, and more preferably three or more. As for the upper limit, 15 or less are preferable, 10 or less are more preferable, and 8 or less are still more preferable.

The molecular weight of the radical polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and still 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 difunctional or higher radical polymerizable monomer containing two or more polymerizable groups, and at least one trifunctional or higher radical polymerizable monomer. It is more preferable. Further, a mixture of a bifunctional radical polymerizable monomer and a trifunctional or higher radical polymerizable monomer may be used. In addition, the number of functional groups of the radical polymerizable monomer means the number of radical polymerizable groups in one molecule.

Specific examples of the radical polymerizable monomer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides, preferably , Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group with a monofunctional or polyfunctional isocyanate or epoxy, or a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid is also suitably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group, monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or tosyloxy groups, etc. Substitution reaction products of unsaturated carboxylic acid esters or amides having a detachable substituent of, and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, as another example, instead of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, and the like. As a specific example, description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred, and these contents are incorporated in this specification.

Further, the radical polymerizable monomer is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropanetri(acryloyloxy) A compound obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as propyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and then (meth)acrylated, Japanese announcement Urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193, Japanese Laid-Open Patent Publication No. 48- Polyester acrylates described in 064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid, etc. And functional acrylates and methacrylates, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. Moreover, a polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth)acrylate and a compound having an ethylenically unsaturated bond is also mentioned.

In addition, as a preferred radical polymerizable monomer other than the above, it has a fluorene ring and is an ethylenically unsaturated bond described in JP 2010-160418A, JP 2010-129825A, JP4364216A, etc. It is also possible to use a compound having two or more groups having or cardo resin.

In addition, as other examples, specific unsaturated compounds described in JP-A-46-043946, JP-A-01-040337, JP-A-01-040336, and JP-A02- The vinylphosphonic acid-based compounds described in No. 025493 can also be mentioned. Moreover, a compound containing a perfluoroalkyl group described in Japanese Laid-Open Patent Publication No. 61-022048 can also be used. Also, the Japanese Adhesion Association, vol. 20, No. 7, 300-308 pages (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A, 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 by reference.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-Open No. Hei 10-062986 together with the specific examples thereof as formulas (1) and (2), (meth)acrylate The compound can also be used as a radical polymerizable monomer.

In addition, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A may also be used as a radical polymerizable monomer, and these contents are incorporated herein by reference.

Examples of the radical polymerizable monomer include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product); Nippon Kayaku Co., Ltd. ), A-TMMT: Shinnakamura Chemical Co., Ltd.), dipentaerythritol penta (meth)acrylate (commercially available, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa (meth) Acrylate (KAYARAD DPHA as a commercial product; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth)acryloyl groups represent an ethylene glycol residue or a propylene glycol residue. A structure that is bonded through is preferable. These oligomer types can also be used.

Commercially available products of radical polymerizable monomers include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 209, 231, 239, DPCA-60, a six-functional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three three isobutyleneoxy chains, Letain oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shinnakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Nippon Kayaku Co., Ltd.) Healing (manufactured by Co., Ltd.), M-306 (manufactured by Toa Kosei Co., Ltd.), and the like.

As the radical polymerizable monomer, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Publication No. Hei 02-032293, and Japanese Publication No. Hei 02-016765. The same urethane acrylates, or ethylene described in Japanese Patent Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, and Japanese Publication No. 62-039418 Urethane compounds having an oxide-based skeleton are also suitable. In addition, as a radical polymerizable monomer, as described in JP-A-63-277653, JP-A-63-260909, and JP-A01-105238, having an amino structure or a sulfide structure in a molecule Compounds can also be used.

The radical polymerizable monomer may be a compound having an acid group such as a carboxyl group and a phosphoric acid group. The radical polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a compound obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group is more preferable. desirable. Particularly preferably, in the compound obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is a compound wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. . As a commercial item, M-510, M-520, etc. are mentioned as a polybasic acid-modified acrylic oligomer manufactured by Toa Kosei Co., Ltd., for example.

The preferred acid value of the radically polymerizable monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When the acid value of the radical polymerizable monomer is in the above range, it is excellent in manufacturing and handling properties, and furthermore, it is excellent in developability. Moreover, the polymerizability is good.

In the resin composition of the present invention, as a radical polymerizable monomer, a monofunctional radical polymerizable monomer can be preferably used from the viewpoint of suppressing warpage by controlling the elastic modulus of the cured film. Examples of monofunctional radical polymerizable monomers include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and carbitol. (Meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene (Meth)acrylic acid derivatives such as glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl Allyl compounds, such as glycidyl ether, diallyl phthalate, and triallyl trimellitate, etc. are used preferably. As the monofunctional radical polymerizable monomer, a compound having a boiling point of 100°C or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

It is preferable that content of a radical polymerizable monomer is 1-60 mass% with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5% by mass or more. It is more preferable that it is 50 mass% or less, and, as for an upper limit, it is more preferable that it is 30 mass% or less. The radical polymerizable monomer may be used singly or in combination of two or more. When using two or more types together, it is preferable that the total amount falls within the above range.

<Other polymerizable compounds>

The resin composition of the present invention may further contain a polymerizable compound (hereinafter, also referred to as another polymerizable compound) other than the radical polymerizable monomer described above. As another polymerizable compound, a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; Epoxy compounds; Oxetane compounds; Benzoxazine compounds.

<<Compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl 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 preferable.

[Formula 14]

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ Represents a hydrogen atom or an organic group ^{having 1 to 10 carbon atoms, and R 107} represents an organic group having 1 to 10 carbon atoms.)

[Formula 15]

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

[Formula 16]

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ is, Represents a hydrogen atom or an organic group ^{having 1 to 10 carbon atoms, and R 507} represents an organic group having 1 to 10 carbon atoms.)

As a specific example of the compound represented by formula (AM4), 46DMOC, 46DMOEP (manufactured by Asahi Yukizai Kogyo Co., Ltd.), 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 (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like.

In addition, as a specific example of the compound represented by 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 (manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by Asahi Yukizai High School Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALACMW-100LM (( Note) Sanwa Chemicals) is mentioned.

<<Epoxy compound (compound having an epoxy group)>>

As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in one molecule. Since the epoxy group undergoes a crosslinking reaction at 200°C or lower and no dehydration reaction resulting from the crosslinking occurs, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective for low-temperature hardening of a composition and suppression of warpage.

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

As an example of an epoxy compound, a bisphenol A type epoxy resin; Bisphenol F type epoxy resin; Alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones, such as polymethyl (glycidyloxypropyl) siloxane, etc. are mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclone (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 trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (manufactured by DIC Corporation) , Rica resin (registered trademark) BEO-60E (Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (made by ADEKA), etc. Among these, epoxy resins containing a polyethylene oxide group are, It is preferable from the viewpoint of suppression of warpage and excellent heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Lika resin (registered trademark) BEO-60E have a polyethylene oxide group. It is preferable because it contains.

<<Oxetane compound (compound having an oxetanyl group)>>

As an oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]Methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. are mentioned. . As a specific example, the Aaronoxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toa Kosei Co., Ltd. can be suitably used, and these may be used alone or in combination of two or more. do.

<<Benzoxazine compound (compound having a benzoxazolyl group)>>

The benzoxazine compound is preferable because degassing does not occur at the time of curing because of a crosslinking reaction resulting from a ring-opening addition reaction, and the occurrence of warpage is suppressed by reducing heat shrinkage.

Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of polyhydroxystyrene resin, and a phenol novolak-type dihydrobenzoxazine compound. Can be lifted. These may be used individually or may mix 2 or more types.

When it contains another polymerizable compound, it is preferable that the content is more than 0 mass% and 60 mass% or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5% by mass or more. It is more preferable that it is 50 mass% or less, and, as for an upper limit, it is more preferable that it is 30 mass% or less. Other polymerizable compounds may be used alone or in combination of two or more. When using two or more types together, it is preferable that the total amount falls within the above range.

<Hot base generator>

It is preferable that the resin composition of this invention contains a hot base generator. The type of the hot base generator is not particularly determined, but includes at least one selected from an acidic compound that generates a base when heated to 40°C or higher, and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0-4. It is preferable to include a hot base generator. _{Here, pKa1 represents the logarithm (-Log 10} Ka) of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later.

By blending such a compound, a cyclization reaction such as a polymer precursor can be performed at a low temperature. In addition, since the hot base generator does not generate a base unless heated, the cyclization of the polymer precursor during storage can be suppressed even when coexisting with the polymer precursor, and the storage stability is excellent.

The hot base generator preferably contains at least one selected from an acidic compound (A1) that generates a base when heated to 40°C or higher, and an ammonium salt (A2) having an anion and an ammonium cation having a pKa1 of 0-4. Do. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the cyclization reaction of the polymer precursor can be accelerated by the base generated from these compounds, and the cyclization of the polymer precursor can be performed at a low temperature. . In addition, in the present specification, with an acidic compound, 1 g of a compound is collected in a container, 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio is water/tetrahydrofuran = 1/4) is added, followed by stirring at room temperature for 1 hour. The obtained solution refers to a compound having a value of less than 7 measured at 20°C using a pH (power of hydrogen) meter.

The base generation temperature of the hot base generator used in the present invention is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the base generation temperature is preferably 190°C or less, more preferably 180°C or less, and still more preferably 165°C or less. The lower limit of the base generation temperature is preferably 130°C or higher, and more preferably 135°C or higher. The base generation temperature is, for example, using differential scanning calorimetry, the compound is heated to 250°C at 5°C/min in an internal pressure capsule, and the peak temperature of the lowest exothermic peak is read, and the peak temperature is determined as base. It can be measured as the generation temperature.

The base generated by the hot base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine has high basicity, the cyclization temperature of the polymer precursor can be lowered. Further, the boiling point of the base generated by the hot base generator is preferably 80°C or higher, more preferably 100°C or higher, and still more preferably 140°C or higher. Moreover, as for the molecular weight of the generated base, 80-2000 are preferable. 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 calculated|required from a structural formula.

In the present embodiment, it is preferable that the acidic compound (A1) contains at least one selected from an ammonium salt and a compound represented by formula (101) or (102) described later.

In this embodiment, it is preferable that the said ammonium salt (A2) is an acidic compound. In addition, the 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 at 40° C. or higher (preferably 120 to 200° C.). It may be a compound other than an acidic compound that generates a base when heated.

In this embodiment, an ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation through a covalent bond, or may have it in addition to the molecule of the ammonium cation, but it is preferable to have it in addition to the molecule of the ammonium cation. In addition, having an anion other than the molecule of the ammonium cation refers to a case where the ammonium cation and the anion are not bound through a covalent bond. Hereinafter, anions other than the molecule of the cationic portion are also referred to as counter anions.

Equation (101) Equation (102)

[Formula 17]

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

It is preferable that the ammonium cation is represented by any one of the following formulas (Y1-1) to (Y1-5).

[Formula 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 meaning as those of 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 to 5.

In this embodiment, it is preferable that the ammonium salt has an anion and an ammonium cation whose pKa1 is 0-4. As for the upper limit of pKa1 of an anion, 3.5 or less are more preferable, and 3.2 or less are still more preferable. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and further, the stability of the resin composition can be improved. When pKa1 is 4 or less, the stability of the hot base generator is good, generation of a base without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, it is difficult to neutralize the generated base, and the cyclization efficiency of the polymer precursor is good.

The kind of anion is preferably one selected from a carboxylic acid anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because the stability of the salt and thermal decomposition can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

The carboxylic acid anion is preferably an anion of a divalent or higher 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 set as a hot base generator which can improve stability, hardenability, and developability of a resin composition more. 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, it is preferable that the carboxylic acid anion is an anion of a carboxylic acid whose pKa1 is 4 or less. As for pKa1, 3.5 or less are more preferable, and 3.2 or less are still more preferable. According to this aspect, the stability of the resin composition can be further improved.

Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and Determination of Organic Structures by Physical Methods (authors: 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, values calculated from structural formulas using software of ACD/pKa (manufactured by ACD/Labs) will be used.

It is preferable that the carboxylate anion is represented by the following formula (X1).

[Formula 19]

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

In this embodiment, the electron withdrawing group means that the Hammett substituent constant σm represents a positive value. Here, σm is the review of Yuho Tsuno, Journal of the Association of Organic Synthetic Chemistry Vol. 23, No. 8 (1965) p. It is described in detail in 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the above document.

Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group (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), and the like. . In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

[Formula 20]

In 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.

In this embodiment, it is preferable that the carboxylic acid anion is represented by the following formula (XA).

Expression (XA)

[Formula 21]

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

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenylimino diacetic acid anion, and oxalic acid anion. These can be used preferably.

The following compounds are mentioned as a specific example of a hot base generator.

[Formula 22]

[Formula 23]

[Formula 24]

The content of the hot base generator is preferably 0.1 to 50% by mass with respect 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 still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One or two or more of the hot base generators can be used. When using two or more types, it is preferable that the total amount is within the above range.

<radical polymerization initiator>

It is preferable that the resin composition of this invention contains a radical polymerization initiator. In particular, when a radical polymerizable group is used or a radical polymerizable compound is used as the polymer precursor, the resin composition of the present invention preferably contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator. It is preferable that the radical polymerization initiator used in the resin composition of the present invention is a photo radical polymerization initiator.

<<optical radical polymerization initiator>>

There is no restriction|limiting in particular as a photo-radical polymerization initiator, It can select suitably from well-known photo-radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferable. Moreover, it may be an activator that generates an active radical by generating a certain action with a photo-excited sensitizer.

It is preferable that the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

As the photo radical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide , Hexaarylbiimidazole, oxime derivatives such as oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds , A metallocene compound, an organic boron compound, and an iron arene complex. For these details, reference can be made to the description of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

As a ketone compound, the compound described in paragraph 0087 of JP-A 2015-087611 A is illustrated, for example, and this content is incorporated in this specification. As a commercial item, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As a photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone initiator described in Japanese Unexamined Patent Publication No. Hei 10-291969 and the acylphosphine oxide initiator described in Japanese Patent Publication No. 4225898 can also be used.

As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (manufactured by BASF) can be used.

As the aminoacetophenone initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

As the aminoacetophenone initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which the maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.

Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Moreover, commercially available products IRGACURE-819 or IRGACURE-TPO (manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

As a photo radical polymerization initiator, more preferably, an oxime compound is mentioned. By using an oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As a specific example of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, and the compound described in JP 2006-342166 A can be used.

Preferred oxime compounds include, for example, compounds of the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) Iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime-based photopolymerization initiator) as a photo radical polymerization initiator. The oxime photopolymerization initiator has a linking group >C=N-O-C(=O)- in a molecule.

[Formula 25]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the optical radical described in Japanese Unexamined Patent Publication No. 2012-014052). The polymerization initiator 2) is also suitably used. In addition, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (Co., Ltd.) ADEKA) can also be used. In addition, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) can be used.

In addition, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in Japanese Laid-Open Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Laid-Open Patent Publication 2014-500852, and Japanese Laid-Open Patent Publication 2013- The compound (C-3) etc. described in paragraph 0101 of 164471 can be mentioned.

As a most preferable oxime compound, an oxime compound which has a specific substituent shown in Unexamined-Japanese-Patent No. 2007-269779, and an oxime compound which has a thioaryl group shown in Unexamined-Japanese-Patent No. 2009-191061, etc. are mentioned.

The photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and a metal from the viewpoint of exposure sensitivity. Rosene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxa A compound selected from the group consisting of a diazole compound and a 3-aryl substituted coumarin compound is preferable.

More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds , A benzophenone compound, an acetophenone compound, and at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound. It is preferable, and it is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is still more preferable.

In addition, the photo radical polymerization initiator is N,N'-tetraalkyl-4,4'-diamino such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Mihiller's ketone). Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morphopoly Aromatic ketones such as no-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, benzyl dies Benzyl derivatives, such as methyl ketal, etc. can also be used. Moreover, a compound represented by the following formula (I) can also be used.

[Formula 26]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, C1-C12 alkoxyl group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, C2-C18 alkyl group and C1-C4 alkyl group interrupted by one or more oxygen atoms Phenyl group substituted with at least one of or biphenyl, R ^I01 is a group represented by formula (II), or is the same group as ^{R I00, and R I02} to R ^I04 are each independently alkyl having 1 to 12 carbon atoms, 1 Alkoxy or halogen of ~12.

[Formula 27]

Wherein, R ~ R ^{I05 I07} is the same as R ^I02 ~ ^I04 R of the formula (I).

In addition, the compound described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as the photo-radical polymerization initiator.

When a photoradical polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% by mass based on the total solid content of the resin composition of the present invention. It is 15 mass %, More preferably, it is 1.0 to 10 mass %. The photo-radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more types of photo radical polymerization initiators are contained, it is preferable that the total is within the above range.

<<Thermal radical polymerization initiator>>

The thermal radical polymerization initiator is a compound that generates a radical by the energy of heat to initiate or accelerate a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be promoted together with the cyclization of the polymer precursor, so that a higher degree of deterioration can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When a thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 30% by mass based on the total solid content of the resin composition of the present invention. It is 15% by mass. Thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing two or more types of thermal radical polymerization initiators, it is preferable that the total is within the above range.

<solvent>

It is preferable that the resin composition of this invention contains a solvent. As the solvent, a known solvent can be used arbitrarily. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -Butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, methyl methoxyacetate) Ethyl oxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionate methyl, 3-alkyloxypropionate ethyl, etc.) For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., 2- Methyl alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2-methylpropionate ethyl (e.g. 2-methoxy-2-methylpropionate methyl, 2- Ethyl ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned as suitable ones.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone as suitable ones.

As aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. are mentioned as a suitable thing, for example.

As sulfoxides, dimethyl sulfoxide is mentioned as a suitable thing, for example.

As amides, suitable examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and the like.

The solvent is also preferably a form in which two or more types are mixed from the viewpoint of improving the properties of the coated surface.

In the present invention, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy methyl propionate, 2-heptane One, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One type of solvent selected from propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferable. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

The content of the solvent is preferably an amount such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, from the viewpoint of coatability, 10 It is more preferable to set it as an amount of -70 mass %, and it is still more preferable to set it as 40 to 70 mass %. The solvent content may be adjusted according to the desired thickness and application method.

The solvent may contain only 1 type, and may contain 2 or more types. When it contains 2 or more types of solvent, it is preferable that the total is the said range.

<migration inhibitor>

It is preferable that the resin composition of this invention further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer.

The migration inhibitor is not particularly limited, but heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine A compound having a ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), a thiourea and a sulfanyl group Compounds having, hindered phenolic compounds, salicylic acid derivatives, and hydrazide derivatives. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Further, an ion trapping agent that captures anions such as halogen ions can also be used.

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

The following compounds are mentioned as a specific example of a migration inhibitor.

[Formula 28]

When the resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass based on the total solid content of the resin composition. It is more preferable. Only one type of migration inhibitor may be used, and two or more types may be used. When there are two or more types of migration inhibitors, it is preferable that the total is within the above range.

<Polymerization inhibitor>

It is preferable that the resin composition of this invention contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p. -Benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol Terdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1- Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3) ,5-tert-butyl)phenylmethane and the like are suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used. Moreover, the following compounds can be used (Me is a methyl group).

[Formula 29]

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, based on the total solid content of the resin composition of the present invention. And more preferably 0.05 to 2.5% by mass. Only one type of polymerization inhibitor may be used, or two or more types of polymerization inhibitors may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above range.

<Metal adhesion improver>

It is preferable that the resin composition of the present invention contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wirings, and the like. As a metal adhesion improving agent, a silane coupling agent etc. are mentioned.

As an example of a silane coupling agent, the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 073 of Japanese Laid-Open Patent Publication 2014-191002, and paragraphs 0063 to 071 of International Publication No. 2011/080992 The compounds described, the compounds described in paragraphs 0060 to 061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, and the compounds described in paragraph 0055 of International Publication No. 2014/097594 are listed. I can. In addition, as described in paragraphs 0050 to 0058 of JP2011-128358A, it is also preferable to use two or more different types of silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Et represents an ethyl group.

[Formula 30]

In addition, as the metal adhesion improving agent, a compound described in paragraphs 0046 to 0049 of JP 2014-186186 A, and a sulfide compound described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used.

The content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass per 100 parts by mass of the polymer precursor. By setting it as the said lower limit or more, the adhesiveness between the cured film and a metal layer after a hardening process becomes good, and by setting it as the said upper limit or less, heat resistance and mechanical properties of the cured film after a hardening process become favorable. Only one type of metal adhesion improving agent may be sufficient, and two or more types may be used. In the case of using two or more types, it is preferable that the total is within the above range.

<Other additives>

The resin composition of the present invention is provided with various additives, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing agents, if necessary, within a range that does not impair the effects of the present invention. A catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like can be blended. When blending these additives, 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, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polymer precursor. 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, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less from the viewpoint of the electric insulation of the cured film.

Thermal acid generators may be used alone or in combination of two or more. When using two or more types, it is preferable that the total amount falls within the above range.

<<Sensitizing pigment>>

The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific activating radiation and enters an electron excited state. The sensitizing dye in an electron excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, so that actions such as electron transfer, energy transfer, and heat generation occur. Thereby, a thermal curing accelerator, a thermal radical polymerization initiator, and a photoradical polymerization initiator cause a chemical change and decompose to generate a radical, an acid, or a base. For details of the sensitizing dye, the description of paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated herein.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition of the present invention. , It is more preferable that it is 0.5-10 mass %. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<<chain transfer agent>>

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the 3rd edition of the Polymer Dictionary (Edition of the Polymer Society, 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These can donate hydrogen to a low-activity radical to generate a radical, or can generate a radical by deprotonating after being oxidized. In particular, a thiol compound 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 has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. It is more preferably ~ 5 parts by mass. One type of chain transfer agent may be sufficient, and two or more types may be used. When the chain transfer agent is 2 or more types, it is preferable that the total is within the above range.

<<surfactant>>

Each type of surfactant may be added to the resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Moreover, the following surfactant is also preferable.

[Chemical Formula 31]

In addition, as a surfactant, the compound 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, and more preferably 0.005 to 1.0% by mass with respect to the total solid content of the resin composition of the present invention. One type of surfactant may be sufficient, and two or more types may be used. When there are two or more surfactants, it is preferable that the total is within the above range.

<<Higher fatty acid derivative>>

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

In addition, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. One type of higher fatty acid derivative may be sufficient, and two or more types may be used. When there are two or more higher fatty acid derivatives, it is preferable that the total is within the above range.

<Restrictions on other substances contained>

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 still more preferably less than 0.6% by mass from the viewpoint of coating surface properties.

The metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, it is preferable that the total of these metals is within the above range.

In addition, as a method of reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention, or a raw material constituting the resin composition of the present invention is selected. On the other hand, a method of performing distillation under conditions in which contamination is suppressed as much as possible by performing filter filtration or lining the inside of the apparatus with polytetrafluoroethylene or the like may be mentioned.

Considering the use of the resin composition as a semiconductor material, the content of the halogen atom is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosiveness. More preferable. Among them, what is present in the form of a halogen ion is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and more preferably less than 0.5 ppm by mass. 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 is in the above range, respectively.

As the container for the resin composition of the present invention, a conventionally known container can be used. In addition, for the purpose of suppressing the incorporation of impurities into the raw material or composition, as the housing container, a multilayer bottle composed of 6 types of 6 layers of resin or a bottle of 6 types of resins in a 7 layer structure may be used. desirable. Examples of such a container include the container disclosed in Japanese Unexamined Patent Application Publication No. 2015-123351.

[Preparation of resin composition]

The resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Further, for the purpose of removing foreign substances such as dust and fine particles in the composition, it is preferable to perform filtration using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be used which was previously washed with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel to be used. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. In the case of filtering a plurality of times, circulation filtration may be employed. Moreover, you may pressurize and perform filtration. In the case of performing filtration by pressurization, the pressure to be pressurized is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, a treatment for removing impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[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, for example, 0.5 µm or more, or 1 µm or more. Moreover, as an upper limit, it can be set as 100 micrometers or less, and can also be set as 30 micrometers or less. It is preferable that the film thickness of the cured film of this invention is 1-30 micrometers.

Two or more layers of the cured film of the present invention may be laminated, and further, 3 to 7 layers may be laminated to form a laminate. The laminate having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a redistribution layer.

As an applicable field of the cured film of the present invention, an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, and the like can be mentioned. In addition, a sealing film, a substrate material (a base film or a coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above is patterned by etching. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervision, CMC Technical Library "Basic and Development of Polyimide Materials" published in November 2011, Japan Polyimide-Aromatic Polymer Research Society/Edition "Latest Polyimide Basics and Applications" N·T·S, August 2010, etc. can be referred.

In addition, the cured film in the present invention can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, use for etching of molded parts, and the production of protective lacquers and dielectric layers in electronics, especially microelectronics.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Examples and Comparative Examples>

The components described in the following table were mixed to obtain a resin composition.

[Table 1]

The raw materials listed in the above table are as follows.

(Polymer precursor)

A-1: Polyimide precursor of the following structure (Mw=25000)

[Formula 32]

A-2: Polybenzoxazole precursor of the following structure (Mw=25000)

[Formula 33]

(Initiator)

B-1: IRGACURE OXE 01 (manufactured by BASF)

B-2: IRGACURE OXE 02 (manufactured by BASF)

B-3: IRGACURE 784 (manufactured by BASF)

B-4: NCI-831 (manufactured by ADEKA Co., Ltd.)

(Polymerizable monomer)

C-1: SR-209 (manufactured by Arkema)

C-2: M-306 (manufactured by Toa Kosei Co., Ltd.)

C-3: A-TMMT (Shin-Nakamura Chemical Industry Co., Ltd. product)

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 sulfoxide

(Hot base generator)

E-1: the following compound

E-2: the following compound

E-3: the following compound

E-4: the following compound

[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 (in the following formula, Et represents an ethyl group.)

[Formula 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>>

A resin composition is spin-coated on a silicon wafer with a copper metal layer formed on its surface so that the film thickness after curing becomes about 10 μm, dried, and then used in a temperature-raising programmable curing furnace (VF-2000 type, manufactured by Koyo Lindbergh). The atmosphere was adjusted under the conditions described in the following table, and heating was performed under the conditions described in the following table to obtain a cured film. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were subjected to nitrogen substitution and adjusted with an oxygen concentration meter (manufactured by Yokogawa Denki).

The obtained cured film was cut into a 3 mm-wide rectangular shape using a dicing saw (DAD3350 type, manufactured by DISCO), and then peeled from the silicon wafer using 46% hydrofluoric acid. The elongation of the cured film peeled from the silicon wafer was measured, and mechanical properties were evaluated based on the following criteria. The elongation of the cured film was measured according to ASTM D882-09 using a tensile tester (UTM-II-20 type, manufactured by Orientech).

A: Elongation of 60% or more

B: elongation of 50% or more and less than 60%

C: elongation of 40 or more and less than 50%

D: elongation less than 40%

<Copper Corrosion>

On a copper substrate, a resin composition is spin-coated so that the film thickness after curing becomes about 10 μm, and after drying, a temperature-raising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindbergh) is used, and the atmosphere in the furnace is shown in the table below. It adjusted to the conditions described, and heated under the conditions described in the following table to obtain a cured film. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were subjected to nitrogen substitution and adjusted with an oxygen concentration meter (manufactured by Yokogawa Denki).

The obtained cured film was cut into a 3 mm-wide rectangular shape using a dicing saw (DAD3350 type, manufactured by DISCO), and then peeled off from the copper substrate using an aqueous ferric chloride solution. The copper substrate after peeling the cured film formed on the surface is taken as the copper substrate 1.

Surface observation (confirmation of discoloration and corrosion) and scanning of the copper substrate (blank) before forming the cured film and the copper substrate (copper substrate 1) after peeling the cured film formed on the surface with an optical microscope (manufactured by Nikon) Cross-sectional observation (confirmation of film thickness fluctuations and irregularities) with an electron microscope (manufactured by Hitachi) was performed, and copper corrosiveness was evaluated according to the following criteria.

A: The copper substrate 1 has no discoloration, corrosion, film thickness fluctuations or irregularities, and has a property equivalent to that of a blank.

B: The copper substrate 1 has a slightly darker purple color than that of the blank, but there are no fluctuations in film thickness or irregularities.

C: Compared to the blank, the copper substrate 1 has a slightly darker purple color, and the copper is slightly damaged and is slightly uneven.

D: Compared to the blank, the copper substrate 1 has a progressive purple color, and the copper is damaged and there are severe irregularities.

[Table 2]

As shown in the above table, the examples were able to form a cured film excellent in mechanical properties.

Claims (10)

A step of forming a film by applying a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radically polymerizable monomer to a substrate,
A method for producing a cured film comprising the step of heat-curing the film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa. The method according to claim 1,
The method for producing a cured film, wherein the atmospheric pressure of the heat-curing step is 0.08 to 0.12 MPa. The method according to claim 1 or 2,
The heat-curing process is a method for producing a cured film, in which the film is heated to 170 to 350°C. The method according to any one of claims 1 to 3,
A method for producing a cured film, comprising a step of exposing the film and a step of developing a film after exposure between the step of forming the film and the step of heat curing. The method according to any one of claims 1 to 4,
The substrate to which the resin composition is applied is a metal substrate or a substrate including a metal layer, a method for producing a cured film. The method according to any one of claims 1 to 5,
A method for producing a cured film, which is a method for producing a cured film for an insulating layer. A resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a radically polymerizable monomer,
A resin composition used in the method for producing a cured film according to any one of claims 1 to 6. A cured film obtained from the resin composition according to claim 7. A method for producing a laminate comprising a step of forming a cured film by the method for producing 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 producing a semiconductor device, including the method for producing a cured film according to any one of claims 1 to 6 or a method for producing a laminate according to claim 9.