CN112888714A - Method for producing cured film, resin composition, cured film, method for producing laminate, and method for producing semiconductor element - Google Patents

Abstract

The present invention provides a method for producing a cured film, which comprises a step of applying a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a radical polymerizable monomer to a substrate to form a film, and a step of heating and curing the film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa. Also provided are a resin composition, a cured film, a method for producing a laminate, and a method for producing a semiconductor element.

Description

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

Technical Field

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

Background

Resins cyclized and cured such as polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation properties, and therefore are suitable for various applications. The use is not particularly limited, but when a semiconductor element for actual mounting is taken as an example, the use as a material for an insulating film or a sealing material or the use of the protective film is exemplified. Also, the film is used as a base film, a cover layer, or the like of a flexible substrate.

Such polyimide resins and the like generally have low solubility in solvents. Therefore, a method of dissolving a polymer precursor before cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor in a solvent is often used. This makes it possible to realize excellent workability and to apply the coating material to a substrate or the like in various forms during the production of the above-described products. Thereafter, the cyclized polymer precursor is heated to enable formation of a cured product. When the cyclized polymer precursor is heated, the heating is performed in an atmosphere with a reduced oxygen concentration, such as a nitrogen atmosphere, in order to prevent oxidation of the substrate.

For example, patent document 1 describes that a photosensitive polyimide resin layer is formed by heating a photosensitive polyimide precursor layer at 200 ℃ to 350 ℃ in an environment where the oxygen concentration is 50ppm or less. Patent document 2 describes that a resin film selected from a photosensitive polyimide precursor and a photosensitive polybenzoxazole precursor is heat-treated in a nitrogen atmosphere, and then heat-treated in an atmosphere containing oxygen.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2010-054451

Patent document 2: japanese patent laid-open publication No. 2004-031564

Disclosure of Invention

Technical problem to be solved by the invention

When a cured film is produced using a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor, it is desirable to lower the heat curing temperature. However, as the heat curing temperature is lowered, the mechanical properties such as elongation of the obtained cured film tend to be lowered. In the inventions described in patent documents 1 and 2, it is also difficult to produce a cured film that satisfies the recent demand level.

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

Means for solving the technical problem

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

<1> a method for producing a cured film, comprising:

a step of applying a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a radical polymerizable monomer to a substrate to form a film; and

and heating and curing the film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa.

<2> the method of <1>, wherein the atmosphere pressure in the step of heating and curing is 0.08 to 0.12 MPa.

<3> the method for producing a cured film according to <1> or <2>, wherein the film is heated to 170 to 350 ℃ in the step of heating and curing.

<4> the method for producing a cured film according to any one of <1> to <3>, wherein a step of exposing the film and a step of developing the exposed film are included between the step of forming the film and the step of curing by heating.

<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 including 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 polyimide precursors and polybenzoxazole precursors, and a radical polymerizable monomer,

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

<8> a cured film obtained from the resin composition <7 >.

<9> a method for producing a laminate, comprising 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, comprising the method for manufacturing a cured film according to any one of <1> to <6> or the method for manufacturing a laminate according to <9 >.

Effects of the invention

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

Detailed Description

The present invention will be described below. In the present specification, "to" means that a range including numerical values before and after the range as a lower limit value and an upper limit value is used.

The following description of the constituent elements of the present invention may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

In the present specification, the label of a group (atomic group) includes both an unsubstituted label and a substituted label, and the unsubstituted label and the substituted label are not described. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure generally include active light or radiation such as far ultraviolet light, extreme ultraviolet light (EUV light), X-ray, and electron beam, which are represented by a bright line spectrum of a mercury lamp or an excimer laser.

In the present specification, "(meth) acrylate" represents both or either of "acrylate" and "methacrylate", "meth (acrylic acid)" represents both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryloyl group" represents both or either of "acryloyl group" and "methacryloyl group".

In the present specification, the term "step" is included in the term not only as an independent step but also as long as the action expected for the step can be achieved even when the step is clearly distinguished from other steps.

The physical property values in the present invention are values at a temperature of 23 ℃ and a gas pressure of 101325Pa or less, unless otherwise specified.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and defined as styrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. In this measurement, THF (tetrahydrofuran) was used as an eluent unless otherwise specified. Unless otherwise specified, the detection is performed by a 254nm wavelength detector using UV rays (ultraviolet rays).

Unless otherwise specified, the temperature in the present invention is 23 ℃.

[ method for producing cured film ]

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

According to the present invention, a cured film having excellent mechanical properties such as elongation can be formed. The reason for this is not clear, but it is presumed that by heating and curing the film in an atmosphere having the above-mentioned predetermined oxygen partial pressure, the amount of oxygen present increases, and the crosslinking density of the radical polymerizable monomer and the polymer precursor is slightly decreased, and the interaction between the polymer precursors is relaxed, and the resistance in the stress direction is increased. In addition, it is generally considered that the polymerization reaction of the radically polymerizable monomer is easily inhibited in the presence of oxygen. Therefore, it is considered that when a film obtained by using a resin composition containing a radical polymerizable monomer is heat-cured, a cured film excellent in mechanical properties such as elongation can be obtained when the oxygen partial pressure during heat-curing is low, but surprisingly, by performing heat-curing of the film in an atmosphere having an oxygen partial pressure in the above range, the mechanical properties such as elongation of the obtained cured film are improved.

Further, since the oxygen partial pressure at the time of heat curing is in the above range, oxidation of the substrate and the like can be suppressed. Therefore, it is particularly effective to use a substrate including a metal layer or a metal substrate as the substrate.

The film production method 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 film production method of the present invention preferably includes the following steps (a) to (d). According to this embodiment, a pattern of a cured film having excellent mechanical properties such as elongation can be formed. The cured film thus formed can be preferably used as an insulating layer. In particular, it can be preferably used as an interlayer insulating film for a rewiring layer.

(a) A step of applying the resin composition to a substrate to form a film (film-forming step),

(b) A step (exposure step) of exposing the film after the film formation step,

(c) A step of developing the exposed film (developing step),

(d) And a step (heat curing step) of heat curing the developed film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa.

Hereinafter, each step will be described in detail.

< film Forming Process >

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

The kind of the substrate can be appropriately determined depending on the application. Examples thereof include inorganic substrates, resin substrates, and resin composite substrates. Examples of the inorganic substrate include a silicon substrate, a silicon nitride substrate, a polycrystalline silicon substrate, a silicon oxide substrate, an amorphous silicon substrate, a glass substrate, a quartz substrate, and a metal substrate. A metal layer of molybdenum, titanium, aluminum, copper, or the like may be formed on the surface of a silicon substrate, a silicon nitride substrate, a polycrystalline silicon substrate, a silicon oxide substrate, an amorphous silicon substrate, a glass substrate, or a quartz substrate. Examples of the resin substrate include substrates made of synthetic resins such as polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene and the like, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins, cyanate resins, crosslinked fumarate diesters, cyclic polyolefins, aromatic ethers, maleimide, olefins, celluloses, episulfide compounds and the like. A metal layer may be formed on the surface of the resin substrate. In the present invention, when a substrate having a metal layer or a metal substrate is used, a cured film which suppresses oxidation of the metal and has excellent mechanical properties such as elongation can be formed.

The method of applying the resin composition to a substrate is preferably coating. Specifically, examples of suitable methods include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an ink jet method. From the viewpoint of uniformity of the thickness of the film (resin composition layer) to be formed, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration or the coating conditions appropriately according to the method, a film (resin composition layer) having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and is preferably spin coating, spray coating, ink jet coating, or the like as long as it is a circular substrate such as a wafer, and is preferably slit coating, spray coating, ink jet coating, or the like as long as it is a rectangular substrate. In the case of spin coating, for example, the coating can be performed at a rotation speed of 500 to 2000rpm for about 10 seconds to 1 minute.

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

< Exposure Process >

The film-forming step may be followed by a step of exposing the film (exposure step). In the exposure step, the film (resin composition layer) is exposed to light through a mask having a predetermined mask pattern by using a stepper, a scanner, or the like, thereby forming a pattern.

The exposure amount is not particularly limited within the range capable of curing the film (resin composition layer), and for example, it is preferably 100 to 10000mJ/cm in terms of exposure energy at a wavelength of 365nm²More preferably, the irradiation is 200 to 8000mJ/cm². The exposure wavelength can be set appropriately within the range of 190 to 1000nm, and is preferably 240 to 550 nm. The exposure wavelength is described in relation to a light source, and examples thereof include (1) a semiconductor laser (having a wavelength of 830nm, 532nm, 488nm, 405nm etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, a g-ray (having a wavelength of 436nm), an h-ray (having a wavelength of 405nm), an i-ray (having a wavelength of 365nm), a broad (3 wavelengths of g, h, and i-rays), (4) an excimer laser, a KrF excimer laser (having a wavelength of 248nm), an ArF excimer laser (having a wavelength of 193nm), an F2 excimer laser (having a wavelength of 157nm), and (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beam, and the like. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and particularly preferably exposed to i-rays. This makes it possible to obtain particularly high exposure sensitivity.

< developing step >

The film production method of the present invention may include a step (developing step) of developing the film (resin composition layer) after exposure. By performing development, an unexposed portion (unexposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as spin immersion, spraying, dipping, or ultrasonic waves can be used.

The development is performed using a developer. The developing solution can be used without particular limitation as long as the unexposed portion (unexposed portion) can be removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be determined as a calculated value by inputting the structural formula by chembidraw (chemibiological diagram).

As the organic solvent, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like, and ethers such as diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol, 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anise ether, limonene, etc., and as sulfoxides, dimethyl sulfoxide, etc., may be suitably cited.

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

The developer is preferably an organic solvent in an amount of 50% by mass or more, more preferably an organic solvent in an amount of 70% by mass or more, and still more preferably an organic solvent in an amount of 90% by mass or more. Further, 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 limited, and the development can be usually carried out at 20 to 40 ℃.

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

< Heat curing step >

In the heat curing step, the film (including a film developed in the exposure step and the development step) is heated. The cyclization reaction of the polymer precursor is carried out by heating to obtain a cured film. The heat curing step can be performed by heating the film in the heating chamber, for example.

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

As a method of adjusting the oxygen partial pressure in the atmosphere in the heat curing step to the above range, there are 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, and the like. Examples of the inert gas include nitrogen, helium, and argon.

For reasons of film stability, the atmospheric pressure in the heat curing step is preferably 0.08 to 0.12MPa, more preferably 0.09 to 0.11 MPa. When the film is heated in the heating chamber, the pressure in the heating chamber corresponds to the atmospheric pressure in the heating/curing step.

Further, the oxygen concentration in the atmosphere in the heat curing step is preferably more than 60 vol ppm and 1500 vol ppm or less. The lower limit is preferably 65 vol ppm or more, more preferably 100 vol ppm or more, and still more preferably 500 vol ppm or more. The upper limit is preferably 1400 vol ppm or more, more preferably 1200 vol ppm or less, and further preferably 1000 vol ppm or less. When the film is heated in the heating chamber, the oxygen concentration in the heating chamber corresponds to the oxygen concentration in the atmosphere in the heat curing step.

The heating temperature (maximum heating temperature) of the film in the heat curing step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, further preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500 ℃ or lower, more preferably 450 ℃ or lower, further preferably 350 ℃ or lower, further preferably 250 ℃ or lower, and further preferably 220 ℃ or lower. The heating temperature (maximum heating temperature) of the film is preferably 170 to 350 ℃.

The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min. The temperature increase rate is set to 1 ℃/min or more, whereby excessive volatilization of the amine can be prevented while ensuring productivity, and the temperature increase rate is set to 12 ℃/min or less, whereby residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and still more preferably 25 to 120 ℃. The temperature at the start of heating is the temperature at the start of the heating step to the maximum heating temperature. For example, when the resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is preferably gradually increased from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the resin composition.

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

In particular, when a multilayer laminate is formed, the film is preferably heated at 180 to 320 ℃, more preferably 180 to 260 ℃ from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but is considered to be because the ethynyl groups of the polymer precursors between the layers are crosslinked with each other by setting the temperature to this temperature.

The heating may be performed in stages. For example, a pretreatment process of raising the temperature from 25 ℃ to 180 ℃ at 3 ℃/min and holding the temperature at 180 ℃ for 60 minutes, raising the temperature from 180 ℃ to 200 ℃ at 2 ℃/min and holding the temperature at 200 ℃ for 120 minutes may be performed. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. These pretreatment steps can improve the film properties. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in two or more stages, and for example, the pretreatment step 1 may be carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 may be carried out at a temperature of 150 to 200 ℃.

Further, the heating and the cooling may be performed, and the cooling rate in this case is preferably 1 to 5 ℃/min.

The cured film can be produced through the above-described steps. Examples of the field to which the cured film can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and a stress buffer film. In addition, a sealing film, a substrate material (a base film, a cover layer, or an interlayer insulating film of a flexible printed circuit board), an insulating film for the above-described actual mounting use, or the like may be patterned by etching. For these uses, for example, reference can be made to Science & Technology co, ltd, "high functionalization and application Technology of polyimide" 4 months 2008, kaki benayu mingming/prison, CMC technical library "foundation and development of polyimide material" 11 months 2011 issue, japan polyimide aromatic system polymer research institute/compilation "latest polyimide foundation and application" NTS, 8 months 2010, and the like. The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use of molded parts, and the production of protective paints and dielectric layers for electronics, particularly microelectronics.

[ method for producing laminate ]

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

The type of the metal layer formed on the surface of the cured film is not particularly limited, and conventional metal types can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper. The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, there are a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined. The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

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

In the method for producing a laminate of the present invention, the curing film forming step and the metal layer forming step may be alternately performed a plurality of times (preferably 2 to 7 times, more preferably 2 to 5 times). In this way, a laminate of a multilayer wiring structure such as resin layer/metal layer/resin layer/metal layer can be produced in which a plurality of cured films (resin layers) and metal layers are alternately laminated.

[ method for manufacturing semiconductor device ]

The method for manufacturing a semiconductor device of the present invention includes the method for manufacturing a cured film of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of the semiconductor device, reference can be made to the description in paragraphs 0213 to 0218 of Japanese patent laid-open No. 2016-027357 and the description of FIG. 1, and these contents are incorporated in the present specification.

[ resin composition ]

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

< Polymer precursor >

The resin composition of the present invention comprises a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. The polymer precursor used in the present invention is preferably a polyimide precursor, because the effects of the present invention can be more significantly obtained.

< polyimide precursor > <

The polyimide precursor preferably contains a structural unit represented by the following formula (1). By adopting such a structure, a composition having more excellent film strength can be obtained.

[ chemical formula 1]

A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents a 2-valent organic group, R¹¹⁵Is represented by the following general formula 4A divalent organic radical, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

A¹And A²Each independently an oxygen atom or NH, preferably an oxygen atom.

<<<R¹¹¹>>>

R¹¹¹Represents an organic group having a valence of 2. Examples of the 2-valent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group containing a combination thereof, and the group is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group containing a combination thereof, and more preferably an aromatic group having 6 to 20 carbon atoms.

R¹¹¹Preferably derived from diamines. The diamine used for producing the polyimide precursor includes a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. One diamine may be used alone, or two or more diamines may be used.

Specifically, the diamine preferably contains a linear 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 combination thereof, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 2]

In the formula, A is preferably a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (-O) -, -S-, and-SO₂The group of (E) is further preferably selected from the group consisting of-CH₂-、-O-、-S-、-SO₂-、-C(CF₃)₂-and-C (CH)₃)₂-a 2-valent radical of the group consisting.

Specific examples of the diamine include those selected from the group consisting of 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl and 3, 3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -diaminodiphenylmethane and 3, 3 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone and 3, 3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide and 3, 3 '-diaminodiphenyl sulfide, 4' -diaminobenzophenone and 3, 3 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl (4, 4' -diamino-2, 2 '-dimethylbiphenyl), 3' -dimethoxy-4, 4 '-diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino-terphenyl, p-phenylene, 4, 4 '-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3' -dimethyl-4, 4 '-diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3' -diethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethyl-4, 4 ' -diaminodiphenylmethane, 4, 4 ' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4, 4 ' -tetraaminobiphenyl, 3 ', 4, 4 ' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 ' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4, 4 ' -dimethyl-3, 3 ' -diaminodiphenylsulfone, 3 ', 5, 5 '-tetramethyl-4, 4' -diaminodiphenylmethane, ethyl 2- (3 ', 5' -diaminobenzoyloxy) methacrylate), 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2, 3, 5, 6-tetramethyl-p-phenylenediamine, 2, 4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, a salt thereof, a pharmaceutically acceptable carrier, and a pharmaceutically acceptable carrier, 4, 4 '-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4 '-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', 5, 5 '-tetramethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2 ', 5, 5', 6, 6 '-hexafluorotolidine, and 4, 4' -diaminotetrabiphenyl.

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

[ chemical formula 3]

Further, as a preferable example, a diamine having at least two or more alkylene glycol units in the main chain can be cited. The diamine is preferably a diamine containing two or more ethylene glycol chains or propylene glycol chains in combination in one molecule, and more preferably a diamine containing no aromatic ring. Specific examples thereof include 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 Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, but the present invention is not limited thereto.

The following shows the structures of 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, and JEFFAMINE (registered trademark) EDR-176.

[ chemical formula 4]

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

From the viewpoint of flexibility of the obtained cured film, R¹¹¹Preferably represented by-Ar⁰-L⁰-Ar⁰-represents. Wherein Ar is⁰Each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L is⁰Represents a single bond, is selected from C1-10 aliphatic hydrocarbon groups which may be substituted by fluorine atoms、-O-、-C(＝O)-、-S-、-S(＝O)₂-, -NHCO-and combinations of these. Preferred ranges are defined as above for A.

From the viewpoint of i-ray transmittance, R¹¹¹Preferred is a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and ready availability, the 2-valent organic group represented by formula (61) is more preferable.

[ chemical formula 5]

R⁵⁰～R⁵⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R⁵⁰～R⁵⁷At least one of which is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

As R⁵⁰～R⁵⁷Examples of the 1-valent organic group in (b) 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), and the like.

[ chemical formula 6]

R⁵⁸And R⁵⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4, 4 '-diaminobiphenyl, 2' -bis (fluoro) -4, 4 '-diaminobiphenyl, 4' -diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more of these may be used in combination.

<<<R¹¹⁵>>>

R in the formula (1)¹¹⁵Represents a 4-valent organic group. The organic group having a valence of 4 preferably contains an aromatic groupThe cyclic 4-valent organic group is more preferably a group represented by the following formula (5) or formula (6).

[ chemical formula 7]

R¹¹²The definition of (A) is the same as that of (A), and the preferable range is the same.

With respect to R in the formula (1)¹¹⁵Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[ chemical formula 8]

R¹¹⁵Represents a 4-valent organic group. R¹¹⁵Is defined as in formula (1) and R¹¹⁵The same is true.

Specific examples of the tetracarboxylic acid dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3, 3 ', 4, 4 ' -biphenyltetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylsulfide tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3, 3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2, 3, 3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2, 3, 3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4, 4 ' -oxydiphthalic acid dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic acid dianhydride, 1, 4, 5, 7-naphthalenetetracarboxylic acid dianhydride, 1, 4, 7-naphthalenetetracarboxylic acid dianhydride, and mixtures thereof, 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3, 4, 4-tetracarboxylic dianhydride, 1, 4, 5, 6-naphthalenetetracarboxylic dianhydride, 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-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1, 2, 3, 4-benzenetetracarboxylic dianhydride, and at least one of alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, as preferable examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can be given.

[ chemical formula 9]

<<<R¹¹³And R¹¹⁴>>>

In the formula (1), R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group. Preferably R¹¹³And R¹¹⁴At least one of them is a repeating unit containing a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.

[ chemical formula 10]

In the formula (III), R²⁰⁰Represents a hydrogen atom or a methyl group, and more preferably a methyl group.

In the formula (III), R²⁰¹An alkylene group having 2 to 12 carbon atoms, -CH₂CH(OH)CH₂Or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, particularlyPreferably 1 to 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). Further, (poly) oxyalkylene group means oxyalkylene group or polyoxyalkylene group.

Preferred R²⁰¹Examples of (3) include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH₂CH(OH)CH₂-, more preferably ethylene, propylene, trimethylene, -CH₂CH(OH)CH₂-。

Particularly preferably R²⁰⁰Is methyl, R²⁰¹Is an ethylene group.

As a preferred embodiment of the polyimide precursor in the present invention, R is¹¹³Or R¹¹⁴Examples of the 1-valent organic group in (b) include an aliphatic group, an aromatic group, an aralkyl group, and the like having 1, 2, or 3 acid groups, preferably one acid group. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acid group, and the aralkyl group has 7 to 25 carbon atoms and has an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is more preferably a hydroxyl group. Namely, R¹¹³Or R¹¹⁴Preferred is a group having a hydroxyl group.

As a group consisting of R¹¹³Or R¹¹⁴The 1-valent organic group represented may preferably be a substituent which improves the solubility of the developer.

From the viewpoint of solubility in an aqueous developer, R¹¹³Or R¹¹⁴More preferred are a hydrogen atom, 2-hydroxybenzyl group, 3-hydroxybenzyl group and 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, R¹¹³Or R¹¹⁴Preferably a 1-valent organic group. The 1-valent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group). The alkyl group may be linear, branched, or cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a camphyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecyl group, a camphyl group, a dicyclohexyl group, and a pinenyl group (pinenyl group). The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described below.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (examples of the cyclic structure of the constituent group include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indene ring, a perylene ring, a condensed pentacene ring, an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, a substituted or unsubstituted aromatic hydrocarbon group,

A ring, a triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (a cyclic structure as a constituent group, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenazine ring, a thianthrene ring, a chromene ring, an oracle ring, a phenoxathiin ring, a phenothiazine ring, or a phenothiazine ring).

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

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

The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A) or (1-B).

[ chemical formula 11]

A¹¹And A¹²Represents an oxygen atom or NH, R¹¹¹And R¹¹²Each independently represents a 2-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, preferably R¹¹³And R¹¹⁴At least one of them is a group containing a radical polymerizable group, and more preferably a radical polymerizable group.

A¹¹、A¹²、R¹¹¹、R¹¹³And R¹¹⁴Independently of one another and in preferred ranges in formula (1) A¹、A²、R¹¹¹、R¹¹³And R¹¹⁴The preferred ranges of (A) are as defined above.

R¹¹²With R in the formula (5)¹¹²The same applies to (1), wherein an oxygen atom is more preferred.

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

In the polyimide precursor, the structural unit represented by formula (1) may be one kind, or two or more kinds. And may contain structural isomers of the structural unit represented by formula (1). The polyimide precursor may contain other types of structural units in addition to the structural unit of formula (1).

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

The polyimide precursor preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.

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 a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a diamine.

In the method for producing a polyimide precursor, an organic solvent is preferably used when the reaction is carried out. One or more organic solvents may be used.

The organic solvent can be appropriately set according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

The production of the polyimide precursor preferably includes a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid deposition can be performed.

< polybenzoxazole precursor >)

The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).

[ chemical formula 12]

R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Are respectively provided withIndependently represents a hydrogen atom or a 1-valent organic group.

R¹²¹Represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least one of an aliphatic group (preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22, more preferably 6 to 14, and particularly preferably 6 to 12 carbon atoms). As a constituent R¹²¹Examples of the aromatic group of (3) include R of the above formula (1)¹¹¹Examples of (3). The aliphatic group is preferably a straight chain aliphatic group. R¹²¹Preferably from 4, 4' -oxodibenzoyl chloride.

In the formula (2), R¹²²Represents a 4-valent organic group. As the 4-valent organic group, R in the above formula (1) is defined¹¹⁵Similarly, the preferred ranges are also the same. R¹²²Preferably from 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group, and is as defined for R in the above formula (1)¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same.

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

The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit, from the viewpoint of suppressing the occurrence of warpage of a cured film accompanying ring closure.

[ chemical formula 13]

Z has a structure a and a structure b, R^1sIs 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), R^2sIs a C1-10 hydrocarbon group (preferably C1-6, more preferably C1-3), R^3s、R^4s、R^5s、R^6sAt leastOne is an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and the remaining is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), and 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, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and a + b is preferably 100 mol%.

In the formula (SL), preferable Z is R in the structure of b^5sAnd R^6sZ being phenyl. 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 gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the effect of reducing the elastic modulus of the polybenzoxazole precursor after dehydration ring closure and suppressing warpage and the effect of improving solubility can be both achieved.

When the precursor contains a diamine residue represented by the formula (SL) as another kind of structural unit, it is preferable to further contain a tetracarboxylic acid residue remaining after removing an acid dianhydride group from the tetracarboxylic dianhydride as a structural unit, from the viewpoint that the alkali solubility can be improved. Examples of such tetracarboxylic acid residues include R in the formula (1)¹¹⁵Examples of (3).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and further preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.

The dispersion degree of the molecular weight 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, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more, relative to the total solid content of the resin composition. 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, still more preferably 98% by mass or less, and still more preferably 95% by mass or less, based on the total solid content of the resin composition.

The resin composition of the present invention may contain only one kind of polymer precursor, or may contain two or more kinds. When two or more are included, the total amount is preferably in the above range.

< radically polymerizable monomer >

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

The number of the radical polymerizable groups of the radical polymerizable compound may be one or two or more, and the radical polymerizable compound preferably has two or more radical polymerizable groups, and more preferably has 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

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

From the viewpoint of developability, the resin composition of the present invention preferably contains at least one 2-or more-functional radical polymerizable monomer having two or more polymerizable groups, and more preferably contains at least one 3-or more-functional radical polymerizable monomer. The polymerizable monomer may be a mixture of a 2-functional radically polymerizable monomer and a 3-or more-functional radically polymerizable monomer. The number of functional groups of the radical polymerizable monomer represents the number of radical polymerizable groups in 1 molecule.

Specific examples of the radical polymerizable monomer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like can also be preferably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having releasable substituent groups such as halogenated groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein by reference.

The radical polymerizable monomer is also preferably a compound having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resulting mixture, JP-B-48-041708, JP-B-50-006034, carbamates of (meth) acrylic acid described in JP-B-51-037193, esters of (meth) acrylic acid, and mixtures thereof, The polyester acrylates described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates as a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also suitable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate.

In addition, as a preferable radical polymerizable monomer other than the above, a compound having a fluorene ring and having two or more ethylenically unsaturated bond-containing groups or a cardo (cardo) resin described in japanese patent application laid-open nos. 2010-160418, 2010-129825, 4364216, and the like can be used.

Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 01-040337, and Japanese patent publication No. 01-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 02-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, compounds described as photopolymerizable monomers and oligomers in Journal of the administration Society of Japan, pages 20 to 308 (1984), and No.7, can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219 can be preferably used, and these contents are incorporated in the present specification.

Further, the following compounds described as the formula (1) and the formula (2) in jp-a-10-062986, together with specific examples thereof, can also be used as radical polymerizable monomers, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resulting mixture.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as radical polymerizable monomers, and these contents are incorporated in the present specification.

Preferred examples of the radical polymerizable monomer include dipentaerythritol triacrylate (commercially available product is KAYARAD-330; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd., A-TMMT: Shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (commercially available product is KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product is KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd.), and a structure in which a (meth) acryloyl group thereof is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomer types of these can also be used.

Commercially available products of the radical polymerizable monomer include, for example, SR-494 (manufactured by Sartomer Company, Inc.) which is a 4-functional acrylate having 4 vinyloxy chains, SR-209, 231, 239 (manufactured by Sartomer Company, Inc.) which is a 2-functional acrylate having 4 vinyloxy chains, DPCA-60 (manufactured by Ltd.) which is a 6-functional acrylate having 6 pentylene oxy chains, TPA-330 (manufactured by Ltd.) which is a 3-functional acrylate having 3 isobutoxy chains, urethane oligomers UAS-10, UAB-140 (PPONINDUSTRIES CO., manufactured by LTD.), NK esters M-40G, NK, 4G, NK esters M-9300, NK esters A-9300, UA-7200 (manufactured by Shin-Nakamura Ltd., DPHA-40 kH), and NiUA-306 (manufactured by Kappu Co., Ltd.) which are manufactured by Ltd, UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical Co., Ltd.), BLEMER PME400(NOF CORPORATION), M-306(TOAGOSEI CO., Ltd.), and the like.

As the radical polymerizable monomer, urethane acrylates such as those disclosed in JP-B-48-041708, JP-B-51-037193, JP-B-02-032293 and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton such as those disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, as the radical polymerizable monomer, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238 can be used.

The radical polymerizable monomer may be a compound having an acid group such as a carboxyl group or a phosphoric acid group. Among the radical polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is more preferable. In particular, among compounds having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydric compound with a non-aromatic carboxylic acid anhydride, a compound in which the aliphatic polyhydric compound is pentaerythritol and/or dipentaerythritol is preferable. Examples of commercially available products include M-510 and M-520 as a polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., Ltd.

The acid value of the radical polymerizable monomer having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical polymerizable monomer is within the above range, the production and handling properties are excellent, and the developability is excellent. Also, the polymerizability was good.

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

The content of the radical polymerizable monomer is preferably 1 to 60% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less. The radical polymerizable monomers may be used alone or in combination of two or more. When two or more kinds are used simultaneously, the total amount is preferably in the above range.

< other polymerizable Compound >

The resin composition of the present invention may further contain a polymerizable compound (hereinafter, also referred to as another polymerizable compound) other than the radical polymerizable monomer. Examples of the other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.

< Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group >)

The compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group is preferably a compound represented by the following formula (AM1), (AM4) or (AM 5).

[ chemical formula 14]

(wherein t represents an integer of 1 to 20, R¹⁰⁴Represents a t-valent organic group having 1 to 200 carbon atoms, R¹⁰⁵Is represented by-OR¹⁰⁶or-OCO-R¹⁰⁷A group represented by R¹⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms¹⁰⁷Represents a carbon atomOrganic groups having a seed number of 1 to 10. )

[ chemical formula 15]

(in the formula, R⁴⁰⁴Represents a 2-valent organic group having 1 to 200 carbon atoms, R⁴⁰⁵Is represented by-OR⁴⁰⁶or-OCO-R⁴⁰⁷A group represented by R⁴⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁴⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 16]

(wherein u represents an integer of 3 to 8, R⁵⁰⁴Represents a u-valent organic group having 1 to 200 carbon atoms, R⁵⁰⁵Is represented by-OR⁵⁰⁶Or, -OCO-R⁵⁰⁷A group represented by R⁵⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁵⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name: ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBISOC-P, DML-PFP, DML-PSBP, DML-MTPC (trade name: Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name: Sanwa Chemical Co., Ltd.), 2, 6-dimethylymethyl-4-t-butyphenol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylymep-4-dimethoxycresol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylymethyl-2-dimethoxycresol (2, 6-dimethoxycresol-2, 6-dimethoxycresol), 6-diacetoxymethyl-p-cresol), and the like.

Specific examples of the compound represented by the formulｃA (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 (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORATION), NIKALAMX-280, NIKAlAC MX-270, and NIKALAC MW-100LM (trade name, manufactured by SanwｃA Chemical Co., Ltd.).

< epoxy Compound (Compound having 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 ℃ or less, and it is difficult to cause film shrinkage since a dehydration reaction derived from crosslinking is not caused. Therefore, by containing the epoxy compound, low-temperature curing and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and preferably 2 to 15.

Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, but the epoxy group-containing silicones 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 (trade name, DIC system, incorporated by reference), RIKARESIN (registered trademark) BEO-60E (registered trademark, Japan trademark), EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (registered trademark), EPICLON, EP-4003S, EP, EP 40026, EP 3, EP 40026, or more, manufactured by ADEKA CORPORATION), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E preferably contain a polyethylene oxide group.

< oxetane Compound (Compound having an oxetanyl group) >

Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxyoxetane, 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, and the like. As a specific example, TOAGOSEI co, a series of ARON oxoetane (for example, OXT-121, OXT-221, OXT-191, and OXT-223) made by ltd can be preferably used, and these may be used alone or two or more kinds may be mixed.

< benzoxazine Compound (Compound having polybenzoxazole group) >

The benzoxazine compound is preferable because the crosslinking reaction due to the ring-opening addition reaction does not generate degassing during curing, and further reduces thermal shrinkage to suppress generation of warpage.

Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (manufactured by Shikoku Chemicals Corporation), a benzoxazine adduct of polyhydroxystyrene resin, and a novolak type dihydrobenzoxazine compound. These may be used alone, or two or more kinds may be mixed.

When other polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less. The other polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used simultaneously, the total amount is preferably in the above range.

< thermal alkali-producing agent >

The resin composition of the present invention preferably contains heatAn alkali-producing agent. The kind of the thermal alkali generator is not particularly limited, and it is preferable that the thermal alkali generator contains at least one selected from an acidic compound which generates an alkali when heated to 40 ℃ or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation. Wherein pKa1 represents the logarithm (-Log) of the dissociation constant (Ka) of the first proton of the acid₁₀Ka), described in detail below.

By blending these compounds, a cyclization reaction of a polymer precursor or the like can be performed at a low temperature. Further, since the thermal alkali generator does not generate an alkali unless heated, even if it coexists with the polymer precursor, cyclization of the polymer precursor during storage can be suppressed, and the storage stability is excellent.

The thermal alkali generator preferably contains at least one selected from an acidic compound (A1) which generates an alkali when heated to 40 ℃ or higher, and an ammonium salt (A2) having an anion with a pKa1 of 0 to 4 and an ammonium cation. Since the acidic compound (a1) and the ammonium salt (a2) generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polymer precursor, and the polymer precursor can be cyclized at a low temperature. In the present specification, the acidic compound means the following compound: compound 1g was collected in a container, 50mL of a mixed solution of ion-exchanged water and tetrahydrofuran (water/tetrahydrofuran: 1/4 by mass) was added, the mixture was stirred at room temperature for 1 hour, and the solution thus obtained was measured by pH (power of hydrogen: pH) at 20 ℃ and was found to be less than 7.

The alkali generation temperature of the thermal alkali generator used in the present invention is preferably 40 ℃ or higher, and more preferably 120 to 200 ℃. The upper limit of the alkali generation temperature is preferably 190 ℃ or less, more preferably 180 ℃ or less, and further preferably 165 ℃ or less. The lower limit of the alkali generation temperature is preferably 130 ℃ or more, more preferably 135 ℃ or more. The base generation temperature can be determined as follows: for example, the compound is heated to 250 ℃ at 5 ℃/min in a pressure-resistant capsule by differential scanning calorimetry, the peak temperature of the exothermic peak with the lowest temperature is read, and the peak temperature is taken as the base generation temperature.

The base generated by the thermal base generator is preferably a secondary or tertiary amine, more preferably a tertiary amine. The tertiary amine is highly basic and therefore enables a lower cyclization temperature of the polymer precursor. The boiling point of the alkali generated by the thermal alkali generator is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 140 ℃ or higher. The molecular weight of the generated alkali is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The value of the 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 the group consisting of an ammonium salt and a compound represented by formula (101) or (102) described below.

In the present embodiment, the ammonium salt (a2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃), or may be a compound other than an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃).

In the present embodiment, the ammonium salt represents a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, may be present outside the molecule of the ammonium cation, but is preferably present outside the molecule of the ammonium cation. The presence of an anion outside the molecule of the ammonium cation indicates that the ammonium cation and the anion are not bonded to each other via a covalent bond. Hereinafter, the anion outside the molecule of the cation portion is also referred to as a counter anion.

Formula (101) formula (102)

[ chemical formula 17]

In the formulae (101) and (102), R¹～R⁶Each independently represents a hydrogen atom or a hydrocarbon group, R⁷Represents a hydrocarbon group. R in the formulae (101) and (102)¹And R²、R³And R⁴、R⁵And R⁶、R⁵And R⁷May be bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-5).

[ chemical formula 18]

In the formulae (Y1-1) to (Y1-5), R¹⁰¹Represents an n-valent organic radical, R¹And R⁷Has the same meaning as that of the formula (101) or the formula (102).

In the formulae (Y1-1) to (Y1-5), Ar¹⁰¹And Ar¹⁰²Each independently represents an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In the present embodiment, the ammonium salt is preferably an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and still more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and the stability of the resin composition can be improved. When pKa1 is 4 or less, the thermal alkali generator has good stability, and generation of alkali without heating can be suppressed, so that the resin composition has good stability. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polymer precursor is good.

The kind of anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion and sulfate anion, and more preferably carboxylate anion from the viewpoint of satisfying both the stability of the salt and the thermal decomposability. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylate anion.

The carboxylate anion is preferably an anion of a 2-valent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a 2-valent carboxylic acid. According to this aspect, the thermal alkali generator can be provided which can further improve the stability, curability, and developability of the resin composition. In particular, the use of the anion of the 2-valent carboxylic acid can further improve the stability, curability, and developability of the resin composition.

In the present embodiment, the carboxylate anion is preferably an anion of a carboxylic acid having pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and still more preferably 3.2 or less. According to this embodiment, the stability of the resin composition can be further improved.

Among them, pKa1 represents the logarithm of the inverse of the dissociation constant of the first proton of an acid, and can be referred to the values described in Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O.A., Nachod, F.C.; compilation: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). As for the compounds not described in these documents, values calculated from the structural formulae using software using ACD/pKa (manufactured by ACD/Labs) were used.

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

[ chemical formula 19]

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

In the present embodiment, the electron-withdrawing group represents a positive value of the Hammett substituent constant σ m. Among them, σ m is described in detail in general, Journal of Synthetic Organic Chemistry, Japan, Vol.23, No. 8 (1965), p.631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.

Examples of the substituent having a positive σ m include CF₃Base (. sigma.m.0.43), CF₃CO group (σ m ═ 0.63), HC ≡ C group (σ m ≡ 0.21), CH group₂CH (σ m) group 0.06, Ac (σ m) group 0.38, MeOCO (σ m) group 0.37, MeCOCH (σ m) CH group 0.21, PhCO (σ m) group 0.34, H₂NCOCH₂And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

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

[ chemical formula 20]

In the formulae (EWG-1) to (EWG-6), R^x1～R^x3Each independently represents 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 the present embodiment, the carboxylate anion is preferably represented by the following formula (XA).

Formula (XA)

[ chemical formula 21]

In the formula (XA), L¹⁰Represents a single bond or an alkylene group, alkenylene group, aromatic group, -NR^XA linking group having a valence of 2 in combination of these, R^XRepresents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

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

Specific examples of the thermal alkali generator include the following compounds.

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

The content of the thermal alkali 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 still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One or more than two kinds of the thermal alkali-producing agents can be used. When two or more are used, the total amount is preferably in the above range.

< free radical polymerization initiator >

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

< photo radical polymerization initiator >

The photo radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light from an ultraviolet region to a visible region is preferable. Also, it may be an active agent that produces some action with a photo-excited sensitizer and generates active radicals.

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

As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include 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 oxides, oxime compounds such as hexaarylbisimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference can be made to the descriptions of paragraphs 0165 to 0182 of Japanese patent laid-open publication No. 2016-027357 and paragraphs 0138 to 0151 of International publication No. 2015/199219, which are incorporated herein.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, the contents of which are incorporated in the present specification. Among commercially available products, KAYACURE DETX (Nippon Kayaku co., ltd.) is also preferably used.

As the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.

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

As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE 369 and IRGACURE 379 (manufactured by BASF) were used.

As the aminoacetophenone-based initiator, the compound described in Japanese patent laid-open No. 2009-191179, which has an absorption maximum wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.

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

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

The photo radical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.

Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > C — N — O — C (═ O) -in the molecule.

[ chemical formula 25]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF Co., Ltd.), and ADEKA OPTOMER N-1919 (photo radical polymerization initiator 2 described in ADEKA CORPORATION, Japanese patent application laid-open No. 2012 and 014052) can also be preferably used. TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Further, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 and 36 to 40 described in paragraph 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in paragraph 0101 of Japanese patent application laid-open No. 2013-164471.

Most preferred oxime compounds include an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and a thioaryl group as shown in Japanese patent laid-open Nos. 2009-191061.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds.

More preferred photo radical polymerization initiators are trihalomethyl triazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, further preferably at least one compound selected from the group consisting of trihalomethyl triazine compounds, d-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, still further preferably metallocene compounds or oxime compounds are used, and still further preferably oxime compounds are used.

Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone or N, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, quinones such as alkylanthraquinone and condensed with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like can be used. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 26]

In the formula (I), R^I00R is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, a phenyl group or a biphenyl group in which an alkenyl group having 2 to 12 carbon atoms is substituted by at least one of an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms and an alkyl group having 1 to 4 carbon atoms, R is^I01Is a group represented by the formula (II), or is a group represented by the formula (II) with R^I00Same radicals, R^I02～R^I04Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[ chemical formula 27]

In the formula, R^I05～R^I07With R of the above formula (I)^I02～R^I04The same is true.

Further, as the photo radical polymerization initiator, a compound described in paragraphs 0048 to 0055 of International publication No. 2015/125469 can be used.

When the photo radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.

< thermal radical polymerization initiator >

The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed, so that higher heat resistance can be achieved. 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 the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, based on the total solid content of the resin composition of the present invention. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.

< solvent >

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

As the esters, preferable esters include, 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 alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.

Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

Preferred ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

As the aromatic hydrocarbons, for example, preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.

The sulfoxide is preferably a sulfoxide such as dimethyl sulfoxide.

Preferable examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.

The solvent is preferably a mixture of two or more types from the viewpoint of improvement of the properties of the coated surface.

In the present invention, it is preferable that the solvent is one or a mixture of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate. Particularly preferably, dimethyl sulfoxide and γ -butyrolactone are used simultaneously.

The content of the solvent is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass, of the total solid content concentration of the resin composition of the present invention, from the viewpoint of coatability. The content of the solvent may be adjusted depending on the desired thickness and coating method.

The solvent may contain only one kind, or may contain two or more kinds. When two or more solvents are contained, the total amount thereof is preferably in the above range.

< migration inhibitor >

The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively inhibit the metal ions originating from the metal layer (metal wiring) from migrating into the resin composition layer.

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

Further, an ion scavenger for scavenging anions such as halide ions can also be used.

As other migration inhibitors, there can be used a rust preventive described in paragraph 0094 of Japanese patent laid-open publication No. 2013-015701, a compound described in paragraphs 0073-0076 of Japanese patent laid-open publication No. 2009-283711, a compound described in paragraph 0052 of Japanese patent laid-open publication No. 2011-059656, a compound described in paragraphs 0114, 0116, and 0118 of Japanese patent laid-open publication No. 2012-194520, a compound described in paragraph 0166 of International publication No. 2015/199219, and the like.

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 28]

When the resin composition contains 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 still more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition. The migration inhibitor may be one kind alone, or two or more kinds thereof. When the migration inhibitor is two or more, it is preferable that the total amount thereof is in the above range.

< polymerization inhibitor >

The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, di-t-butylphenol, p-t-butyl-p-cresol, pyrogallol, p-butylphenol, p-benzoquinone, diphenyl, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used. Further, the following compound (Me is methyl) can also be used.

[ chemical formula 29]

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the resin composition of the present invention. The polymerization inhibitor may be one kind alone, or two or more kinds thereof. When the polymerization inhibitor is two or more, the total amount thereof is preferably in the above range.

< Metal adhesion improver >

The resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improver include a silane coupling agent.

Examples of the silane coupling agent include a compound described in paragraph 0167 of International publication No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and a compound described in paragraph 0055 of International publication No. 2014/097594. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[ chemical formula 30]

Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935 can be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer precursor. When the lower limit value is set to the above-mentioned lower limit value or more, the adhesion between the cured film and the metal layer after the curing step is good, and when the upper limit value is set to the below-mentioned upper limit value, the heat resistance and the mechanical properties of the cured film after the curing step are good. The metal adhesion improver may be one kind alone, or two or more kinds thereof. When two or more kinds are used, the total of them is preferably in the above range.

< other additives >

The resin composition of the present invention can contain, as necessary, various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like, as long as the effects of the present invention are not impaired. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the composition.

< thermal acid generating agent >

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. The thermal acid generator is contained in an amount of 0.01 part by mass or more, whereby the crosslinking reaction and the cyclization of the polymer precursor are promoted, and thus the mechanical properties and the medicine resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.

The thermal acid generator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

< sensitizing dye >

The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation to become an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and functions such as electron transfer, energy transfer, heat generation, and the like are generated. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which 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, and still more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition of the present invention. The sensitizing pigment may be used alone or in combination of two or more.

< chain transfer agent > <

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These radicals can be generated by supplying hydrogen to a low-activity radical to generate a radical, or by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

Further, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International publication No. 2015/199219 can be used.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be one kind only, or two or more kinds. When the chain transfer agent is two or more, the total amount thereof is preferably in the above range.

< surfactant >)

Various surfactants may be added to the resin composition of the present invention in order to further improve coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Also, the following surfactants are also preferable.

[ chemical formula 31]

Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International publication No. 2015/199219 can be used.

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, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the resin composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total amount thereof is preferably in the above range.

< higher fatty acid derivative >

In order to prevent inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so as to be locally present on the surface of the composition during drying after application.

Further, as the higher fatty acid derivative, a compound described in paragraph 0155 of international publication No. 2015/199219 can 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. The higher fatty acid derivative may be one kind alone, or two or more kinds thereof. When the number of the higher fatty acid derivatives is two or more, the total number is preferably in the above range.

< restrictions on other contained substances >

The moisture content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass, from the viewpoint of the properties of the coated surface.

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

Further, as a method for reducing metal impurities unexpectedly contained in the resin composition of the present invention, there can be mentioned a method in which a raw material having a small metal content is selected as a raw material constituting the resin composition of the present invention, the raw material constituting the resin composition of the present invention is filtered through a filter, and the inside of the apparatus is lined with polytetrafluoroethylene and distilled under conditions in which contamination is suppressed as much as possible.

In view of the use as a semiconductor material and the corrosion of wiring, the content of the halogen atom in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm. Among them, the amount of the halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is in the above-mentioned range.

As the container for the resin composition of the present invention, a conventionally known container can be used. In addition, for the purpose of suppressing the contamination of impurities into the raw material or the composition, a multilayer bottle having an inner wall of the container made of 6 kinds of 6-layer resins, preferably a bottle having a 7-layer structure made of 6 kinds of resins is used as the storage container. Examples of such a container include those disclosed in Japanese patent laid-open 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.

For the purpose of removing foreign matter such as dust and fine particles in the composition, filtration using a filter is preferably performed. The pore diameter of the filter 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 previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in parallel or in series. When a plurality of filters are used, filters having different pore sizes or different materials may be used in combination. Also, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a circulating filtration. Also, filtration may be performed after pressurization. When the filtration is performed after the pressurization, the pressure for the pressurization is preferably 0.05MPa or more and 0.3MPa or less.

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[ cured film ]

Next, the cured film of the present invention will be described.

The cured film of the present invention is obtained from the resin composition of the present invention. The thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less. The 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 with 2 or more layers, and further laminated with 3 to 7 layers to form a laminate. The laminate having 2 or more layers of the cured films of the present invention preferably has a metal layer between the cured films. These metal layers can be preferably used as metal wirings such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and a stress buffer film. In addition, a sealing film, a substrate material (a base film, a cover layer, or an interlayer insulating film of a flexible printed circuit board), an insulating film for the above-described actual mounting use, or the like may be patterned by etching. For these uses, for example, reference can be made to Science & Technology co, ltd, "high functionalization and application Technology of polyimide" 4 months 2008, kaki benayu mingming/prison, CMC technical library "foundation and development of polyimide material" 11 months 2011 issue, japan polyimide aromatic system polymer research institute/compilation "latest polyimide foundation and application" NTS, 8 months 2010, and the like.

The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use of molded parts, and the production of protective paints and dielectric layers for electronics, particularly microelectronics.

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the processing steps, and the like described in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

< examples and comparative examples >

Resin compositions were obtained by mixing the components shown in the following tables.

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

(Polymer precursor)

A-1: polyimide precursor having the following structure (Mw 25000)

[ chemical formula 32]

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

[ chemical formula 33]

(initiator)

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

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

B-3: IRGACURE 784 (manufactured by BASF corporation)

B-4: NCI-831 (manufactured by ADEKA CORPORATION)

(polymerizable monomer)

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

C-2: m-306(TOAGOSEI CO., LTD. manufactured)

C-3: A-TMMT (Shin Nakamura Chemical Co., Ltd., manufactured by Ltd.)

C-4: KAYARAD DPHA (Ni ppon Kayaku Co., Ltd.)

(solvent)

D-1: n-methyl pyrrolidone

D-2: lactic acid ethyl ester

D-3: gamma-butyrolactone

D-4: dimethyl sulfoxide

(thermal alkali-producing agent)

E-1: the following compounds

E-2: the following compounds

E-3: the following compounds

E-4: the following compounds

[ chemical formula 34]

(silane coupling agent)

F-1: the following compound (in the following formula, Et represents ethyl.)

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

F-3: the following compound (in the following formula, Et represents ethyl.)

[ chemical formula 35]

(polymerization inhibitor)

G-1: 1, 4-benzoquinones

G-2: 4-methoxyphenol

(migration inhibitor)

H-1: 1, 2, 4-triazoles

H-2: 1H-tetrazole

< evaluation >

< evaluation of mechanical Properties >

On a silicon wafer having a copper metal layer formed on the surface thereof, a resin composition was spin-coated so that the cured film thickness became about 10 μm, dried, and then heated in a temperature-programmed curing oven (VF-2000 type, KOYO therm SYSTEMS co., ltd.) under conditions described in the following table while adjusting the atmosphere in the oven to the conditions described in the following table, thereby obtaining a cured film. The oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were adjusted by nitrogen substitution and oxygen concentration meter (manufactured by Yokogawa Electric Corporation).

The obtained cured film was cut into a short strip of 3mm width by a cutter (model DAD3350, manufactured by DISCO Corporation), and then peeled from the silicon wafer with 46% hydrofluoric acid. The elongation of the cured film peeled from the silicon wafer was measured, and the mechanical properties were evaluated by the following criteria. The elongation of the cured film was measured by using a tensile tester (model UTM-II-20, ORIENTEC Co., LTD) according to ASTM D882-09.

A: elongation of 60% or more

B: the elongation is more than 50 percent and less than 60 percent

C: the elongation is more than 40 percent and less than 50 percent

D: the elongation is less than 40 percent

< copper Corrosion Property >

The resin composition was spin-coated on a copper substrate until the cured film thickness became about 10 μm, dried, and then subjected to a temperature-programmed curing oven (VF-2000 type, manufactured by KOYO thermal SYSTEMS co., ltd.) to adjust the atmosphere in the oven to the conditions shown in the following table, and heated under the conditions shown in the following table, thereby obtaining a cured film. The oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were adjusted by nitrogen substitution and oxygen concentration meter (manufactured by Yokogawa Electric Corporation).

The obtained cured film was cut into a short strip of 3mm width by a cutter (model DAD3350, manufactured by DISCO Corporation), and then peeled from the copper substrate with an aqueous solution of ferric chloride. The copper substrate after peeling off the cured film formed on the surface was used as the copper substrate 1.

With respect to the copper substrate (bare substrate) before the cured film was formed and the copper substrate (copper substrate 1) after the cured film formed on the surface was peeled, surface observation (confirmation of discoloration/corrosion) by an optical microscope (manufactured by NIKON CORPORATION) and cross-sectional observation (confirmation of film thickness variation/unevenness) by a scanning electron microscope (manufactured by Hitachi, ltd.) were performed, and copper corrosivity was evaluated according to the following criteria.

A: the copper substrate 1 had the same properties as the bare substrate, without discoloration/corrosion, film thickness variation, and unevenness.

B: the copper substrate 1 was slightly darker in purple color than the bare substrate, but had no variation in film thickness or unevenness.

C: the copper substrate 1 was slightly darker in purple than the bare substrate, and the copper was slightly damaged and slightly uneven.

D: the copper substrate 1 is turned into dark purple compared with the bare substrate, and further, copper is damaged to have severe unevenness.

[ Table 2]

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

Claims (10)

1. A method of manufacturing a cured film, comprising:

a step of applying a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a radical polymerizable monomer to a substrate to form a film; and

and heating and curing the film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa.

2. The method for producing a cured film according to claim 1,

the atmosphere pressure in the heating and curing process is 0.08MPa to 0.12 MPa.

3. The method for producing a cured film according to claim 1 or 2, wherein,

in the step of heating and curing, the film is heated to 170 to 350 ℃.

4. The method for producing a cured film according to any one of claims 1 to 3,

the step of forming a film and the step of heat curing include a step of exposing the film and a step of developing the exposed film.

5. The method for producing a cured film according to any one of claims 1 to 4,

the substrate to which the resin composition is applied is a metal substrate or a substrate including a metal layer.

6. The method for manufacturing a cured film according to any one of claims 1 to 5, which is a method for manufacturing 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 radical polymerizable monomer,

the resin composition is used for the method for producing a cured film according to any one of claims 1 to 6.

8. A cured film obtained from the resin composition of claim 7.

9. A method for producing a laminate, comprising a step of forming a cured film by the method for producing a cured film according to any one of claims 1 to 6, and a step of forming a metal layer on a surface of the cured film.

10. A method for manufacturing a semiconductor element, comprising the method for manufacturing a cured film according to any one of claims 1 to 6 or the method for manufacturing a laminate according to claim 9.