KR102637283B1 - Method for producing a cured film, a method for producing a resin composition, a cured film, a laminate, and a method for producing a semiconductor device - Google Patents

Abstract

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, and forming the film at an oxygen partial pressure of 6 to 150 Pa. A method for producing a cured film comprising the step of curing by heating in a phosphorus atmosphere. A method for producing a resin composition, a cured film, a laminate, and a method for producing a semiconductor device.

Description

Method for producing a cured film, a method for producing a resin composition, a cured film, a laminate, and a method for producing a semiconductor device

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

Resins cured by cyclization, such as polyimide resin and polybenzoxazole resin, are excellent in heat resistance and insulation, and are therefore applied to a variety of applications. The use is not particularly limited, but for example, in semiconductor devices for mounting, it can be used as an insulating film or sealing material, or as a protective film. Additionally, it is also used as a base film or cover lay for flexible substrates.

Such polyimide resins generally have low solubility in solvents. Therefore, a method of dissolving the polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor, in a solvent is often used. As a result, excellent handling properties can be realized, and when manufacturing each product as described above, it can be applied and processed into various forms on a substrate or the like. Thereafter, the polymer precursor may be heated to cyclize and form a cured product. Additionally, when heating and cyclizing the polymer precursor, heating is performed in an atmosphere with reduced oxygen concentration, such as a nitrogen atmosphere, in order to prevent oxidation of the substrate.

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 where the oxygen concentration is 50 ppm or less. Additionally, Patent Document 2 describes heat-treating a resin film selected from a photosensitive polyimide precursor or a photosensitive polybenzoxazole precursor in a nitrogen atmosphere and then heat-treating it again in an atmosphere containing oxygen.

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

When 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 lower the heat curing temperature further. However, as the heat curing temperature is lowered, mechanical properties such as elongation of the resulting cured film tend to decrease. Even 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.

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

According to the present inventor's examination, 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 used as the resin composition, and this resin composition is It was found that a cured film with excellent mechanical properties could be obtained by heat-curing the film obtained using the film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa, and the present invention was completed. The present invention provides the following.

<1> 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;

A method of producing a cured film comprising the step of curing the film by heating in an atmosphere with an oxygen partial pressure of 6 to 150 Pa.

<2> The method for producing a cured film according to <1>, wherein the atmospheric pressure in the heat curing process is 0.08 to 0.12 MPa.

<3> The method of producing a cured film according to <1> or <2>, wherein the heat curing step is heating the film to 170 to 350°C.

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

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

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

<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 the step of forming a cured film by the method for producing a cured film according to any one of <1> to <6>, and the step of forming a metal layer on the surface of the cured film.

<10> A method for manufacturing a semiconductor device, including the method for manufacturing a cured film according to any one of <1> to <6>, or the method for manufacturing a laminated body according to <9>.

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

Below, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used to mean that the numerical values written before and after it are included as the lower limit and the upper limit.

Description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include those that do not have a substituent as well as those that have a substituent. For example, an “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

In this specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, light used for exposure generally includes actinic rays or radiation such as the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In this specification, “(meth)acrylate” represents both “acrylate” and “methacrylate” or either one, and “(meth)acrylic” represents “acrylic” and “methacrylate”. It represents both or either one, and "(meth)acryloyl" represents either or both of "acryloyl" and "methacryloyl".

In this specification, the word "process" is included in this term not only as an independent process, but also in cases where the process cannot be clearly distinguished from other processes if the desired effect of the process is achieved.

Unless otherwise specified, the physical property values in the present invention are taken at a temperature of 23°C and an atmospheric pressure of 101325 Pa.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are calculated using, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard column HZ-L and TSKgel Super HZM-M as the column. , can be obtained by using 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, unless otherwise specified, detection is performed using a UV ray (ultraviolet ray) detector with a wavelength of 254 nm.

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

[Method for producing cured film]

The method for producing a cured film of the present invention includes the 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. (Film formation process) and a process of curing the film by heating in an atmosphere with an oxygen partial pressure of 6 to 150 Pa (heat curing process).

According to the present invention, a cured film with excellent mechanical properties such as elongation can be formed. Although the detailed reason is unclear, by performing heat curing of the film in an atmosphere with the predetermined oxygen partial pressure, the amount of oxygen present increases, which slightly lowers the crosslink density between the radically polymerizable monomer and the polymer precursor, and the interaction between the polymer precursors It is presumed that this was achieved by alleviating this and increasing resistance in the stress direction. Additionally, it was generally thought that the polymerization reaction of radically polymerizable monomers was likely to be inhibited in the presence of oxygen. For this reason, when heat-curing a film obtained using a resin composition containing a radically polymerizable monomer, it was thought that a cured film with superior mechanical properties such as elongation could be obtained if the oxygen partial pressure during heat-curing was lower. It is surprising that mechanical properties, such as elongation, of the obtained cured film were able to be improved by carrying out the process in an atmosphere with an oxygen partial pressure in the above range.

In addition, since the oxygen partial pressure during heat curing is within the above range, oxidation of the substrate, etc. can be suppressed. For this reason, it is particularly effective when the substrate includes a metal layer or when a metal substrate is used.

The method for producing a film of the present invention preferably includes a step of exposing the film and a step of developing the exposed film between the step of forming the film (film forming step) and the step of heat curing (heat curing step). That is, the method for producing the film of the present invention preferably includes the following steps (a) to (d). According to this aspect, it is possible to form a pattern of a cured film excellent in mechanical properties such as elongation. The cured film formed in this way can be suitably used as an insulating layer. In particular, it can be preferably used as an interlayer insulating film for a redistribution layer.

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

(b) After the film formation process, a process of exposing the film (exposure process),

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

(d) A process of heat-curing the developed film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa (heat-curing process).

Hereinafter, each process will be described in detail.

<Film formation process>

In the film formation 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 radically polymerizable monomer is applied to the substrate to form a film. Details of the resin composition will be described later.

The type of substrate can be appropriately determined depending on the intended use. Examples include inorganic substrates, resin substrates, and resin composite material substrates. Examples of inorganic substrates include silicon substrates, silicon nitride substrates, polysilicon substrates, silicon oxide substrates, amorphous silicon substrates, glass substrates, quartz substrates, and metal substrates. A metal layer such as molybdenum, titanium, aluminum, or copper may be formed on the surfaces of the silicon substrate, silicon nitride substrate, polysilicon substrate, silicon oxide substrate, amorphous silicon substrate, glass substrate, and quartz substrate. As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyldiglycol carbonate, and polyamide. , polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, Examples include substrates made of synthetic resins such as silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic ether, maleimide, olefin, cellulose, and episulfide compound. A metal layer may be formed on the surface of the resin substrate. In the present invention, even when a substrate having a metal layer or a metal substrate is used, a cured film with excellent mechanical properties such as elongation can be formed while suppressing oxidation of the metal, so it is particularly effective when using such a substrate.

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

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

<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 process, the film (resin composition layer) can be exposed in a pattern by exposing it 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 particularly determined as long as the film (resin composition layer) can be cured, but, for example, irradiation of 100 to 10,000 mJ/cm ² is preferable in terms of exposure energy at a wavelength of 365 nm, and irradiation of 200 to 8,000 mJ/cm ² is preferable. It is more desirable to do so. 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 related 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 405nm), i-line (wavelength 365nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet rays; Examples include EUV (wavelength 13.6 nm) and (6) electron beam. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with i-line is especially preferable. Thereby, 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 the film (resin composition layer) after exposure. By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as the desired pattern can be formed, and for example, development methods such as puddle, spray, immersion, and ultrasonic waves can be adopted.

Development is performed using a developing solution. The developer can be used without particular restrictions 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 the organic solvent. In the present invention, the developing solution preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by entering the structural formula in ChemBioDraw.

Organic solvents include esters, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate) , ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. ( 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, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy -2-methylethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers, for example 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, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrroli. Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene, and as sulfoxides, dimethyl sulfoxide.

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

It is preferable that 50 mass% or more of the developing solution is an organic solvent, more preferably 70 mass% or more of an organic solvent, and even more preferably 90 mass% or more of an organic solvent. Additionally, 100% by mass of the developer may be an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly determined, but can usually be carried out at 20 to 40°C.

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

<Heat curing process>

In the heat curing process, the film (the developed film if it includes the exposure process and the development process) is heated. By heating, a cyclization reaction of the polymer precursor proceeds and a cured film is obtained. The heat curing process can be performed, for example, by heating the film in a heating chamber.

In the present invention, the membrane is heated in an atmosphere where the oxygen partial pressure is 6 to 150 Pa. The upper limit of the oxygen partial pressure during the heating process is preferably 120 Pa or less, more preferably 100 Pa or less, and still more preferably 60 Pa or less for the reason of suppressing corrosion of the substrate. Moreover, 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 it is easy to obtain a cured film with mechanical properties such as better elongation. Additionally, when heating a film in a heating chamber, the oxygen partial pressure in the heating chamber corresponds to the oxygen partial pressure in the atmosphere of the heat curing process.

Methods for adjusting the oxygen partial pressure in the atmosphere of the heat-curing process to the above range include a method of adjusting the oxygen partial pressure by replacing the gas in the atmosphere in the heating chamber with an inert gas, a method of adjusting the oxygen partial pressure by reducing the pressure in the heating chamber, etc. For example, for reasons of film stability, a method of adjusting the oxygen partial pressure by replacing the gas in the atmosphere in the heating chamber with an inert gas is preferable. Examples of inert gases include nitrogen, helium, and argon.

The atmospheric pressure in the heat curing process is preferably 0.08 to 0.12 MPa, more preferably 0.09 to 0.11 MPa, for reasons of film stability. Additionally, when heating the film within a heating chamber, the pressure within the heating chamber corresponds to the atmospheric pressure of the heat curing process.

Moreover, it is also preferable that the oxygen concentration in the atmosphere of the heat curing process 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 even 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 even more preferably 1000 ppm by volume or less. Additionally, when heating a film in a heating chamber, the oxygen concentration in the heating chamber corresponds to the oxygen concentration in the atmosphere of the heat curing process.

The heating temperature (maximum heating temperature) of the film in the heat curing process 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 even more preferable, and it is even more preferable that it is 170°C or higher. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, more preferably 350°C or lower, still more preferably 250°C or lower, and even more preferably 220°C or lower. Additionally, the heating temperature (maximum heating temperature) of the film is preferably 170 to 350°C.

Heating is preferably performed at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the highest heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of amine can be prevented while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, residual stress in the cured film can be alleviated.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when a resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is gradually raised from a temperature that is, for example, 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 even more preferably 30 to 240 minutes.

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

Heating may be performed in stages. For example, a pretreatment process such as raising the temperature from 25°C to 180°C at 3°C/min, holding at 180°C for 60 minutes, raising the temperature at 2°C/min from 180°C to 200°C, and holding at 200°C for 120 minutes. You may do this. The heating temperature as a pretreatment process is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to process while irradiating ultraviolet rays as described in U.S. Patent Publication No. 9159547. It is possible to improve the properties of the membrane through this pretreatment process. The pretreatment process may be performed for a short period of time, such as 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be performed in two or more steps, for example, pretreatment step 1 may be performed in the range of 100 to 150°C, and then pretreatment step 2 may be performed in the range of 150 to 200°C.

Additionally, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

A cured film can be manufactured through the above process. Fields in which the cured film can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, patterns may be formed by etching sealing films, substrate materials (base films, cover lays, and interlayer insulating films of flexible printed circuit boards), or insulating films for mounting purposes as described above. Regarding these uses, for example, Science & Technology Co., Ltd., "High-functionalization and application technology of polyimide", April 2008, Masaaki Kakimoto/supervision, CMC Technical Library, "Basics and development of polyimide materials", published in November 2011, You can refer to the Japanese Polyimide and Aromatic Polymer Research Society/edit, “Latest Polyimide Basics and Applications,” N·T·S, August 2010. In addition, the cured film can also be used for the production of plates such as offset plates or screen plates, for use in etching of molded parts, and for the production of protective lacquers and dielectric layers in electronics, especially microelectronics.

[Method for manufacturing laminate]

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

There is no particular limitation on the type of the metal layer formed on the surface of the cured film, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, and copper and aluminum are more preferred. Copper is preferred, and copper is more preferred. The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these are contemplated. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can 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 part.

In the method for producing a laminated body 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 by the method for producing a cured film of the present invention described above again after the metal layer forming step.

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

[Method for manufacturing semiconductor devices]

The manufacturing method of the semiconductor device of this invention includes the manufacturing method of the cured film of this invention mentioned above, or the manufacturing method of the laminated body of this invention mentioned above. As a specific example of the semiconductor device, the description in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to, and these contents are incorporated in this specification.

[Resin composition]

Next, the resin composition used in the film production method of the present invention will be explained.

<Polymer precursor>

The resin composition of the present invention contains a polymer precursor selected from polyimide precursors and polybenzoxazole precursors. The polymer precursor used in the present invention is preferably a polyimide precursor because it is easier to significantly obtain the effects of the present invention.

<<Polyimide precursor>>

As a polyimide precursor, it is preferable to include a structural unit represented by the following formula (1). By using such a structure, a resin composition with more excellent film strength can be 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 It 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 straight-chain or branched aliphatic groups, cyclic aliphatic groups, and groups consisting of aromatic groups, heteroaromatic groups, or combinations thereof, and straight-chain aliphatic groups with 2 to 20 carbon atoms and 3 to 20 carbon atoms. A branched aliphatic group, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a combination thereof is preferable, and an aromatic group with 6 to 20 carbon atoms is more preferable.

R ¹¹¹ is preferably derived from diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

Specifically, the diamine preferably contains a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. And, it is more preferable that it is diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following.

[Formula 2]

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ - , -NHCO-, and a combination thereof is preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, and -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 para-phenylenediamine, 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'-diaminodiphenylsulfone. 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) C) 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'-diaminoctafluorobiphenyl, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl) -10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5 -Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3 '-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethylmethacryl Late, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2 , 4,6-trimethyl-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)tetradecafluoro Heptane, 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) diphenyl sulfone , 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexa Fluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl , 2,2', 5,5', 6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

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

[Formula 3]

Also, diamines having at least two or more alkylene glycol units in the main chain can also be cited as preferred examples. Preferably, it is a diamine containing two or more of one or both of the ethylene glycol chain and the propylene glycol chain in one molecule, and more preferably, it is a diamine containing no aromatic ring. As specific examples, Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR -148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy )propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but are not limited to these.

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.

R ¹¹¹ is preferably represented as -Ar ⁰ -L ⁰ -Ar ⁰ - from the viewpoint of flexibility of the resulting cured film. However, Ar ⁰ is each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and especially preferably 6 to 10 carbon atoms), 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. The preferable range has the same meaning as A described above.

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

[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. am.

Examples of the monovalent organic group represented by 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. You 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 diamine compounds 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, and 4,4'-diaminooctafluorobiphenyl. One type of these may be used, or two or more types may be used in combination.

<<<R ¹¹⁵ >>>

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

[Formula 7]

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

The tetravalent organic group represented by R ¹¹⁵ in Formula (1) specifically includes the tetracarboxylic acid residue remaining after the acid dianhydride group is removed from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[Formula 8]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in equation (1).

Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-dianhydride. Phenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4 '-Diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-Diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-Biphenyltetracarboxylic dianhydride, 2,3 ,3',4'-benzophenone tetracarboxylic 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 At least one selected from (3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetracarboxylic acid dianhydride, and alkyl derivatives thereof having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms The species is illustrated.

Additionally, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples.

[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 due to the action of a radical, and a group having an ethylenically unsaturated bond is a preferred example. Examples of the group having an ethylenically unsaturated bond include vinyl group, allyl group, (meth)acryloyl group, and 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 (the alkylene group has 1 to 12 carbon atoms) preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred; the number of repetitions is preferably 1 to 12, more preferred 1 to 6, and particularly preferred 1 to 3. Additionally, (poly)oxyalkylene group means an oxyalkylene group or polyoxyalkylene group.

Examples of suitable R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group. , dodecamethylene group, -CH ₂ CH(OH)CH ₂ -, and ethylene group, propylene group, trimethylene group, -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, the monovalent organic group of R ¹¹³ or R ¹¹⁴ is an aliphatic group, an aromatic group, and an arylalkyl group having 1, 2, or 3 acid groups, preferably 1 acid group. etc. can be 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 can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves solubility in a developing solution is preferably used.

In terms of solubility in an aqueous developer, it is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a straight-chain or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.

The number of carbon atoms in the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic form). The alkyl group may be linear, branched, or cyclic. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, and iso. Propyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic alkyl group or a polycyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group, and pinenyl group. I can hear it. Moreover, as the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described below is preferable.

As an aromatic group, specifically, a substituted or unsubstituted aromatic hydrocarbon group (cyclic structures constituting the group include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, and a hepthalene ring. , indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.) or 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, and benzofuran. Ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring. , phenanthroline ring, cyanthrene ring, chromene ring, xanthene ring, phenoxathyine ring, phenothiazine ring, or phenazine ring).

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

Additionally, for the purpose of improving 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(paraminophenyl)octamethylpentasiloxane, and the like.

The structural unit represented by formula (1) is preferably 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 It is preferable that at least one of ¹¹³ and R ¹¹⁴ is a group containing a radical polymerizable group, and it is more preferable that it is a radical polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same preferred range as the preferred range of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1) am.

The preferable range of R ¹¹² has the same meaning as R ¹¹² in formula (5), and it is more preferable that it is an oxygen atom.

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

In the polyimide precursor, the number of structural units represented by formula (1) may be one, or two or more types may be used. Moreover, structural isomers of the structural unit represented by formula (1) may be included. Moreover, the polyimide precursor may also 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, the polyimide precursor is a structural unit in which 50 mol% or more, particularly 70 mol% or more, and especially 90 mol% or more of the total structural units are structural units represented by formula (1). It is exemplified. As an upper limit, 100 mol% or less is practical.

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

The dispersion degree of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

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

In the method for producing a polyimide precursor, it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one, and two or more types may be used.

The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

When producing a polyimide precursor, it is preferable to include a step of precipitating solids. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor is soluble, such as tetrahydrofuran.

<<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, and 1-6 are especially preferable) and an aromatic group (carbon number is 6-22 are preferable, and 6-14 are more preferable) A group containing at least one of 6 to 12 is preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the aliphatic group, a straight-chain 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 the above formula (1), and its preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and have the same preferable range.

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

Since the occurrence of warping of the cured film due to ring closure can be suppressed, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit.

[Formula 13]

Z has an a structure 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 1 carbon atom. ~10 hydrocarbon groups (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 6 carbon atoms) 22, more preferably 6 to 18 carbon atoms, especially preferably 6 to 10 carbon atoms), and the remainder is hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, especially Preferably, it is an organic group having 1 to 6 carbon atoms, and each may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z 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 formula (SL), preferred examples of Z include those where R ^5s and R ^6s in the b structure are phenyl groups. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight within the above range, it is possible to achieve both the effect of lowering the elastic modulus after dehydration ring closure of the polybenzoxazole precursor and suppressing bending and the effect of improving solubility.

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, the tetracarboxylic acid residue remaining after removal of the acid dianhydride group from tetracarboxylic dianhydride is used to improve alkali solubility. It is desirable to include more as. An example of such a tetracarboxylic acid residue is R ¹¹⁵ in formula (1).

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

The molecular weight dispersion degree of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass, based on the total solid content of the resin composition. It is 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. Moreover, 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, and still more preferably 98% by mass or less, based on the total solid content of the resin composition. , it is more preferable that it is 95% by 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 of polymer precursor. 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 radically polymerizable monomer, a compound having radical polymerizability can be used. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. The radical polymerizable group is preferably a (meth)acryloyl group.

The number of radically polymerizable groups in the radically polymerizable monomer may be 1 or 2 or more, but the radically polymerizable compound preferably has 2 or more radically polymerizable groups, and more preferably has 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

The molecular weight of the radically 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 radically polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the resin composition of the present invention preferably contains at least one type of difunctional or higher radical polymerizable monomer containing two or more polymerizable groups, and at least one type of trifunctional or higher radical polymerizable monomer. It is more preferable. Additionally, it may be a mixture of a difunctional radically polymerizable monomer and a trifunctional or more radically polymerizable monomer. In addition, the number of functional groups of a radically polymerizable monomer means the number of radically polymerizable groups in one molecule.

Specific examples of radically polymerizable monomers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably , esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reactions between unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or sulfanyl groups and monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional Dehydration condensation reactants with carboxylic acids are also suitably used. In addition, addition reactants between unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or epoxy group and monofunctional or polyfunctional alcohols, amines, or thiols, as well as halogen groups, tosyloxy groups, etc. Substitution reactants of unsaturated carboxylic acid esters or amides with a dissociable substituent and monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. Also, as another example, instead of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and these contents are incorporated in this specification.

Also, the radical polymerizable monomer is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylol propane tri(acryloyloxy) Propyl)ether, tri(acryloyloxyethyl)isocyanurate, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and then turning it into (meth)acrylate, Japanese notice. Urethane (meth)acrylates as described in Patent Publication No. 48-041708, Japanese Patent Application Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193, Japanese Patent Application Publication No. 48- Polyester acrylates described in No. 064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, and epoxy acrylates that are a reaction product of epoxy resin and (meth)acrylic acid. Functional acrylates, methacrylates, and mixtures thereof can be mentioned. Additionally, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Moreover, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be mentioned.

Preferred radically polymerizable monomers other than those described above include those described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc., which have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups or cardo resin.

In addition, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, and Japanese Patent Publication No. 02-02. Vinylphosphonic acid-based compounds described in No. 025493 can also be mentioned. Additionally, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Also, Journal of the Japan Adhesive Association, vol. 20, no. 7, pages 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

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

In addition, ethylene oxide or propylene oxide is added to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Patent Application Laid-Open No. 10-062986, followed by (meth)acrylate. The compound can also be used as a radically polymerizable monomer.

In addition, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as radically polymerizable monomers, the contents of which are incorporated herein by reference.

As the radically polymerizable monomer, dipentaerythritol triacrylate (as a commercial product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) ) agent, A-TMMT: manufactured by Shinnakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) Acrylates (commercially available products include KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; A-DPH; manufactured by Shinnakamura Chemical Co., Ltd.), and their (meth)acryloyl group is an ethylene glycol residue or a propylene glycol residue. A structure in which the two are joined together is preferable. These oligomeric types can also be used.

Commercially available radical polymerizable monomers include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, manufactured by Sartomer, and SR-, a bifunctional methacrylate with four ethyleneoxy chains, manufactured by Sartomer. 209, 231, 239, DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, and TPA-330, a trifunctional acrylate with three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd. Lethene oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shinnakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Kagaku Co., Ltd.), Blemmer PME400 (manufactured by Nippon Kayaku Co., Ltd.) Examples include Chiyu Co., Ltd.) and M-306 (made by Toa Kosei Co., Ltd.).

As the radically polymerizable monomer, it is described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. The same urethane acrylates and ethylene described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Urethane compounds having an oxide-based skeleton are also suitable. In addition, as a radically polymerizable monomer, it has an amino structure or a sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. Compounds can also be used.

The radically polymerizable monomer may be a compound having an acid group such as a carboxyl group or a phosphoric acid group. The radically 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 an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group is more preferable. desirable. Particularly preferably, in the compound obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is a compound wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. . Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The preferred acid value of the radically polymerizable monomer having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radically polymerizable monomer is within the above range, manufacturing and handling properties are excellent, and further development properties are excellent. Additionally, it has good polymerizability.

The resin composition of the present invention can preferably use a monofunctional radically polymerizable monomer as a radical polymerizable monomer from the viewpoint of suppressing bending by controlling the elastic modulus of the cured film. Monofunctional radically 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 and 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 are preferably used. As monofunctional radically polymerizable monomers, compounds having a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure.

The content of the radically polymerizable monomer is preferably 1 to 60% by mass based on the total solid content of the resin composition of the present invention. As for the lower limit, 5 mass% or more is more preferable. As for the upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less. Radical polymerizable monomers may be used individually, or two or more types may be mixed. 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 polymerizable compounds (hereinafter also referred to as other polymerizable compounds) other than the radically polymerizable monomers described above. Other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

<<Compounds having a hydroxymethyl group, alkoxymethyl group or 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 , and 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. 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 , and R ⁵⁰⁶ represents, It 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.)

Specific examples of compounds represented by formula (AM4) include 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 (made by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (made by Sanwa Chemical Co., Ltd.), Examples include 2,6-dimethoxymethyl-4-t-buthylphenol, 2,6-dimethoxymethyl-p-cresol, and 2,6-diacetoxymethyl-p-cresol.

Additionally, specific examples of compounds represented by formula (AM5) include 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 Kagaku Kogyo Co., Ltd.), TM-BIP-A (manufactured by Asahi Yukizai Kogyo Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALACMW-100LM (( (made by Sanwa Chemical Co., Ltd.) can be mentioned.

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

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200°C or lower, and since the dehydration reaction resulting from crosslinking does not occur, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective in suppressing low-temperature curing and warping of the composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and bending can be suppressed. A polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and it is preferable that the number of structural units is 2 to 15.

Examples of epoxy compounds include 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; Silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane may be mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (manufactured by DIC Corporation) , Rika Resin (registered trademark) BEO-60E (Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (manufactured by ADEKA Co., Ltd.), etc. Among these, epoxy resin containing a polyethylene oxide group, It is preferable because it suppresses warping and has excellent heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Rika Resin (registered trademark) BEO-60E contain a polyethylene oxide group. It is preferable because it contains

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

Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. . As a specific example, the Aaronoxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, either alone or in a mixture of two or more types. do.

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

Benzoxazine compounds are preferable because they prevent degassing during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and also reduce heat shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include B-a type benzoxazine, B-m type benzoxazine (manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzoxazine compound. I can hear it. These may be used individually, or two or more types may be mixed.

When containing other polymerizable compounds, the content thereof is preferably greater than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. As for the lower limit, 5 mass% or more is more preferable. As for the upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less. Other polymerizable compounds may be used individually, or two or more types may be mixed. When using two or more types together, it is preferable that the total amount falls within the above range.

<Thermobase generator>

The resin composition of the present invention preferably contains a heat base generator. As a thermobase generator, the type is not specifically determined, but includes at least one type selected from acidic compounds that generate a base when heated above 40°C, and ammonium salts having an anion and an ammonium cation with a pKa1 of 0 to 4. It is preferable to include a thermobase generator. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, and details will be described later.

By mixing such a compound, a cyclization reaction of a polymer precursor or the like can be performed at low temperature. In addition, since the thermobase generator does not generate a base unless heated, even if it coexists with the polymer precursor, cyclization of the polymer precursor during storage can be suppressed, and storage stability is excellent.

The thermobase generator preferably contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40°C or higher, and an ammonium salt (A2) having an anion and an ammonium cation with a pKa1 of 0 to 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 promoted by the base generated from these compounds, and the cyclization of the polymer precursor can be performed at a low temperature. . In this specification, an acidic compound refers to collecting 1 g of the compound in a container, adding 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio water/tetrahydrofuran = 1/4), and stirring at room temperature for 1 hour. It refers to a compound in which the value of the solution obtained as measured at 20°C using a pH (power of hydrogen) meter is less than 7.

The base generation temperature of the thermobase 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 lower, more preferably 180°C or lower, and still more preferably 165°C or lower. 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 determined by, for example, using differential scanning calorimetry, heating the compound to 250°C in a pressure-resistant capsule at 5°C/min, reading the peak temperature of the lowest exothermic peak, and determining the peak temperature as the base temperature. It can be measured as the temperature at which it occurs.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since tertiary amines have high basicity, the cyclization temperature of the polymer precursor can be lowered. Additionally, the boiling point of the base generated by the heat base generator is preferably 80°C or higher, more preferably 100°C or higher, and even more preferably 140°C or higher. Moreover, the molecular weight of the base generated is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value obtained from the structural formula.

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

In this embodiment, the ammonium salt (A2) is preferably 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). Any compound other than an acidic compound that generates a base when heated may be used.

In this embodiment, ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bound to any part of the ammonium cation through a covalent bond, and may be contained in addition to the ammonium cation molecule, but is preferably contained in addition to the ammonium cation molecule. Additionally, having an anion other than the ammonium cation molecule refers to a case where the ammonium cation and anion are not bonded through a covalent bond. Hereinafter, the anion other than the cation moiety molecule is also called a counter anion.

Equation (101) Equation (102)

[Formula 17]

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

The ammonium cation is preferably 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 formula (101) or (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, the ammonium salt preferably has an anion and an ammonium cation with a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is within 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 thermal base generator is good, base generation without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is difficult to neutralize, and the cyclization efficiency of the polymer precursor is good.

The type of anion is preferably one selected from carboxylic acid anion, phenol anion, phosphate anion, and sulfuric acid anion, and carboxylic acid anion is more preferable because it can achieve both salt stability and thermal decomposability. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.

The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and is more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermobase generator that can further improve the stability, curability, and developability of the resin composition. In particular, by using the anion of divalent carboxylic acid, the stability, curability, and developability of the resin composition can be further improved.

In this embodiment, the carboxylic acid anion is preferably an anion of carboxylic acid with a pKa1 of 4 or less. As for pKa1, 3.5 or less is more preferable, and 3.2 or less is 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 is referred to in Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; edited by Braude , E. A., Nachod, F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R. M. C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software is used.

The carboxylic acid anion is preferably represented by the following formula (X1).

[Formula 19]

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

In this embodiment, an electron withdrawing group means that Hammett's substituent constant σm shows a positive value. Here, σm is summarized in Yuho Tsuno's review, Journal of Organic Synthetic Chemistry, Volume 23, Number 8 (1965), p. It is explained in detail in 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents 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), and 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), etc. . Additionally, 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, the carboxylic acid anion is preferably represented by the following formula (XA).

Equation (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 , represents an alkenyl group or an aryl group.

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

Specific examples of heat base generators include the following compounds.

[Formula 22]

[Formula 23]

[Formula 24]

The content of the thermobase generator is preferably 0.1 to 50% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. As for the upper limit, 30 mass % or less is more preferable, and 20 mass % or less is more preferable. One type or two or more types of thermobase 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>

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

<<Optical radical polymerization initiator>>

The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator that has photosensitivity to light from the ultraviolet region to the visible region is preferred. Additionally, it may be an activator that produces an active radical by producing some kind of effect with the photoexcited sensitizer.

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

As a radical photopolymerization initiator, any known compound can be used arbitrarily. 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. , oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds. , metallocene compounds, organic boron compounds, iron arene complexes, etc. For these details, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, the content of which is incorporated herein by reference. As a commercially available product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As radical photopolymerization initiators, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine oxide-based 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-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

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

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

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

As a radical photopolymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it becomes possible to improve the exposure latitude more effectively. Oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

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

[Formula 25]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF) and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd.; optical radicals described in Japanese Patent Application Publication No. 2012-014052). Polymerization initiator 2) is also suitably used. Additionally, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Ackles NCI-831 and Adeka Ackles NCI-930 (made by Changzhou Tronly New Electronic Materials Co., Ltd.) (made by ADEKA) can also be used. Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

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

The most preferable oxime compounds include oxime compounds having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, oxime compounds having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like.

From the viewpoint of exposure sensitivity, the radical photopolymerization initiator is trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, and metal. locene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complex and its salts, halomethyloxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

More preferable radical photopolymerization initiators include trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and 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, it is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is even more preferable.

In addition, the radical photopolymerization initiator is N,N'-tetraalkyl-4,4'-diamino such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), etc. Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholy Aromatic ketones such as no-propanone-1, quinones condensed with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyldimethylsiloxane. Benzyl derivatives such as methyl ketal 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 with 1 to 20 carbon atoms, an alkyl group with 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxyl group with 1 to 12 carbon atoms, a phenyl group, an alkyl group with 1 to 20 carbon atoms, Alkoxyl group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, alkyl group with 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and alkyl group with 1 to 4 carbon atoms. is a phenyl group or ^biphenyl substituted with ^at least ^{one of} ~12 alkoxy or halogen.

[Formula 27]

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

Moreover, as a radical photopolymerization initiator, the compound described in paragraphs 0048-0055 of International Publication No. 2015/125469 can also be used.

When a radical photopolymerization 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 0.5 to 0.5% by mass, based on the total solid content of the resin composition of the present invention. It is 15 mass%, and more preferably 1.0 to 10 mass%. The radical photopolymerization initiator may contain only one type, and may contain two or more types. When containing two or more types of radical photopolymerization initiators, it is preferable that the total is within the above range.

<<Thermal radical polymerization initiator>>

A thermal radical polymerization initiator is a compound that generates radicals using heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be advanced along with cyclization of the polymer precursor, making it possible to achieve a higher degree of heat resistance. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554.

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. The thermal radical polymerization initiator may contain only one type, and may contain two 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>

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

As esters, for example, 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 alkyloxyacetate (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, methoxyacetate) ethyl oxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. ( For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (for example, 2- Methyl alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy propionate) methyl, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2- Suitable examples include ethyl ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Suitable examples include propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate.

Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

Suitable examples of sulfoxides include dimethyl sulfoxide.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

It is also preferable that two or more types of solvents are mixed from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptane. 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 consisting of two or more types is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of applicability, the solvent content is preferably such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, and 10 It is more preferable to set it as ~70 mass%, and it is still more preferable to set it to 40-70 mass%. The solvent content can be adjusted depending on the desired thickness and application method.

Only one type of solvent may be contained, and two or more types may be contained. When containing two or more types of solvents, it is preferable that the total is within the above range.

<Migration inhibitor>

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

There are no particular restrictions on the migration inhibitor, but heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine) Compounds having a ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group A compound having a, hindered phenol-based compound, salicylic acid derivative-based compound, and hydrazide derivative-based compound can be mentioned. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, compounds described in paragraph 0052 of JP2011-059656, The compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

Specific examples of migration inhibitors include the following compounds.

[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 desirable. The number of migration inhibitors may be one, or 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>

The resin composition of the present invention preferably contains a polymerization inhibitor. Polymerization inhibitors include, for example, 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, etc. are suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. Additionally, 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, and more preferably 0.02 to 3% by mass, based on the total solid content of the resin composition of the present invention. And, it is more preferable that it is 0.05 to 2.5 mass%. The number of polymerization inhibitors may be one, or two or more types may be used. When there are two or more polymerization inhibitors, it is preferable that the total is within the above range.

<Metal adhesion improver>

The resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, and the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992. Examples include the compounds described, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014/097594. You can. Additionally, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different types of silane coupling agents. Moreover, it is also preferable to use the following compounds as the silane coupling agent. In the formula below, Et represents an ethyl group.

[Formula 30]

Additionally, the metal adhesion improver may be a compound described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186, or a sulfide-based compound described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer precursor. By setting it above the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The number of metal adhesion improving agents may be one, or two or more types may be used. When 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 may contain various additives, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, and hardeners, as necessary, within the range that does not impair the effects of the present invention. Catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomerates, etc. can be mixed. 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, per 100 parts by mass of the polymer precursor. Since the crosslinking reaction and cyclization of the polymer precursor are promoted by containing 0.01 parts by mass or more of the thermal acid generator, the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

Only one type of heat acid generator may be used, or two or more types may be used. 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 electronic excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and this content is incorporated herein by reference.

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 to 10 mass%. Sensitizing dyes may be used individually, or two or more types may be used in combination.

<<Chain Transfer System>>

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Dictionary of Polymers, 3rd edition (Polymer Society edition, 2005), pages 683-684. As a chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate radicals by donating hydrogen to low-activity radicals, or by deprotonating them after being oxidized. In particular, thiol compounds can be preferably used.

Additionally, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

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. ~5 parts by mass is more preferable. There may be only one type of chain transfer agent, or two or more types may be used. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.

<<Surfactant>>

Various types of surfactants may be added to the resin composition of the present invention from the viewpoint of further improving applicability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. Additionally, the following surfactants are also preferred.

[Formula 31]

Additionally, the surfactant may be a compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

When the resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the resin composition of the present invention. The number of surfactants may be one, or two or more types may be used. When there are two or more types of surfactants, it is preferable that the total is within the above range.

<<Advanced fatty acid derivatives>>

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

Additionally, 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 contains 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. There may be only one type of high-grade fatty acid derivative, or two or more types may be used. When there are two or more types of higher fatty acid derivatives, it is preferable that the total is within the above range.

<Restrictions on other contained substances>

The water 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 the properties of the coated surface.

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

Additionally, as a method of reducing metal impurities unintentionally contained in the resin composition of the present invention, raw materials with a low metal content are selected as the raw materials constituting the resin composition of the present invention, or raw materials constituting the resin composition of the present invention are selected. Methods such as performing filter filtration or lining the inside of the device with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible are examples.

Considering the use of the resin composition of the present invention as a semiconductor material, the halogen atom content 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 corrosion. It is more desirable. Among them, the amount of the halogen ion present in the state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, are each within the above range.

As a container for containing the resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, for the purpose of suppressing the incorporation of impurities into the raw materials or composition, a multi-layer bottle whose inner wall is made of 6 types of 6-layer resin, or a bottle with a 7-layer structure of 6 types of resin can be used. desirable. Examples of such containers include those described in Japanese Patent Application Publication No. 2015-123351.

[Preparation of resin composition]

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

Additionally, 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 hole 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 one that has been previously washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected and used in series or parallel. When using multiple types of filters, filters with different pore diameters or materials may be used in combination. Additionally, various materials may be filtered multiple times. When filtering multiple times, circular filtration may be used. Additionally, filtration may be performed under pressure. When performing filtration by pressurizing, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, treatment to remove 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. For example, 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, and can be 1 μm or more. Additionally, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less. The film thickness of the cured film of the present invention is preferably 1 to 30 μm.

The cured film of the present invention may be laminated in two or more layers, and further in 3 to 7 layers, to form a laminate. The laminated body which has two or more layers of cured films of this 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.

Applicable fields of the cured film of the present invention include insulating films of semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, patterns may be formed by etching sealing films, substrate materials (base films, cover lays, and interlayer insulating films of flexible printed circuit boards), or insulating films for mounting purposes as described above. Regarding these uses, for example, Science & Technology Co., Ltd., "High-functionalization and application technology of polyimide", April 2008, Masaaki Kakimoto/supervision, CMC Technical Library, "Basics and development of polyimide materials", published in November 2011, You can refer to the Japanese Polyimide and Aromatic Polymer Research Society/edit, “Latest Polyimide Basics and Applications,” N·T·S, August 2010.

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

Example

The present invention will be described in more detail below with reference to examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed appropriately as long as they do not deviate from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. “Part” and “%” are based on mass, unless otherwise specified.

<Examples and Comparative Examples>

A resin composition was obtained by mixing the components listed in the table below.

[Table 1]

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

(polymer precursor)

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

[Formula 32]

A-2: Polybenzoxazole precursor with 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 (made 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 (manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

C-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(solvent)

D-1: N-methylpyrrolidone

D-2: Ethyl lactate

D-3: γ-Beautyrolactone

D-4: dimethyl sulfoxide

(thermal 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 formula below, Et represents an ethyl group.)

F-2: The following compound (in the formula below, Et represents an ethyl group.)

F-3: The following compound (in the formula below, 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 machine characteristics>>

A resin composition is spin-coated on a silicon wafer with a copper metal layer formed on the surface so that the cured film thickness is about 10 μm, dried, and then cured in the furnace using a temperature-increasing programmable cure furnace (VF-2000 type, manufactured by Koyo Lindbergh). The atmosphere was adjusted to the conditions shown in the table below, heating was performed under the conditions shown in the table below, and a cured film was obtained. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were replaced with nitrogen and adjusted with an oxygen concentration meter (manufactured by Yokogawa Denki).

The obtained cured film was cut into a rectangular shape with a width of 3 mm 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 the 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 Orientec).

A: Reliability is over 60%

B: Reliability is 50% or more but less than 60%

C: Elasticity is 40 or more but less than 50%

D: Elasticity less than 40%

<Copper corrosiveness>

A resin composition was spin-coated on a copper substrate so that the film thickness after curing was about 10 μm, dried, and then using a temperature rising programmable cure furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.), the atmosphere in the furnace was as shown in the table below. The conditions were adjusted to those described, heating was performed under the conditions described in the table below, and a cured film was obtained. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were replaced with nitrogen and adjusted with an oxygen concentration meter (manufactured by Yokogawa Denki).

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

Surface observation (confirmation of discoloration and corrosion) using an optical microscope (made by Nikon) and scanning of a copper substrate (blank) before forming a cured film and a copper substrate (copper substrate 1) after peeling off the cured film formed on the surface. Cross-sectional observation (confirmation of film thickness fluctuations and irregularities) was performed using an electron microscope (manufactured by Hitachi), and copper corrosion resistance was evaluated based on the following standards.

A: Copper substrate 1 has no discoloration, corrosion, film thickness variation, or irregularities, and has the same properties as the blank.

B: Copper substrate 1 has a slightly darker purple color compared to the blank, but there is no variation in film thickness or unevenness.

C: Copper substrate 1 has a slightly darker purple color compared to the blank, and the copper is slightly damaged and has some irregularities.

D: Copper substrate 1 is dark purple compared to the blank, and the copper is damaged and has severe irregularities.

[Table 2]

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

Claims (11)

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;
A method of producing a cured film comprising the step of curing the film by heating in an atmosphere where the oxygen partial pressure is 6 to 150 Pa. In claim 1,
A method for producing a cured film, wherein the atmospheric pressure in the heat curing process is 0.08 to 0.12 MPa. In claim 1 or claim 2,
The heat curing step is a method of producing a cured film in which the film is heated to 170 to 350°C. In claim 1 or claim 2,
A method for producing a cured film, comprising a step of exposing the film and a step of developing the exposed film between the step of forming the film and the step of curing by heating. In claim 1 or claim 2,
A method of producing a cured film, wherein the substrate to which the resin composition is applied is a metal substrate or a substrate containing a metal layer. In claim 1 or claim 2,
A method for producing a cured film, which is a method for producing a cured film for an insulating layer. In claim 1,
A method for producing a cured film, wherein the atmospheric pressure of the heat-curing process is 0.08 to 0.12 MPa, and the oxygen concentration in the atmosphere of the heat-curing process is 60 ppm by volume or more and 1,400 ppm by volume or less. A resin composition comprising a polyimide precursor and a radically polymerizable monomer,
A resin composition used in the method for producing a cured film according to claim 1 or 2. A cured film obtained from the resin composition according to claim 8. A method of producing a laminate, comprising a step of forming a cured film by the method of producing a cured film according to claim 1 or 2, and a step of forming a metal layer on the surface of the cured film. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured film according to claim 1 or 2.