TWI819121B - Method for manufacturing cured film, method for manufacturing cured film, laminated body, and method for manufacturing semiconductor element - Google Patents

Abstract

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體之樹脂組成物適用於基板來形成膜之步驟和將膜在氧分壓為6~150Pa的氣氛下加熱硬化之步驟。亦提供一種樹脂組成物、硬化膜、積層體的製造方法及半導體元件的製造方法。 The present invention provides a method for manufacturing a cured film, which includes adding a polyimide precursor selected from polyimide precursors and polybenzoyl

A resin composition of at least one polymer precursor in the group of azole precursors and a radically polymerizable monomer is applied to a substrate to form a film and the film is heated and hardened in an atmosphere with an oxygen partial pressure of 6 to 150 Pa steps. Also provided are a method for manufacturing a resin composition, a cured film, a laminated body, and a method for manufacturing a semiconductor element.

Description

Method for manufacturing cured film, method for manufacturing cured film, and laminated body and manufacturing methods of semiconductor components

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體之樹脂組成物之硬化膜的製造方法。又，本發明有關一種樹脂組成物、硬化膜、積層體的製造方法及半導體元件的製造方法。 The present invention relates to a method for using a compound selected from the group consisting of polyimide precursors and polybenzoyl

A method for producing a cured film of a resin composition of at least one polymer precursor from the group of azole precursors and a radically polymerizable monomer. Furthermore, the present invention relates to a method for manufacturing a resin composition, a cured film, a laminated body, and a method for manufacturing a semiconductor element.

唑樹脂等環化並硬化之樹脂的耐熱性及絕緣性優異，因此適用於各種用途。該用途並無特別限定，但若以實際安裝用半導體元件為例，則可舉出作為絕緣膜或密封材料的素材或該保護膜的利用。又，亦用作撓性基板的基底膜或覆蓋層等。 Polyimide resin, polybenzo

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

唑前驅物的狀態溶解於溶劑中之方法。藉此，能夠實現優異的操作性，且在製造如上述各產品時能夠以各種形態塗佈於基板等進行加工。之後，加熱環化聚合物前驅物而能夠形成硬化產品。又，加熱環化聚合物前驅物時，為了防止基板的氧化等，在氮氣氛下等降低氧濃度之氣氛下進行加熱。 Such polyimide resins generally have low solubility in solvents. Therefore, the state of the polymer precursor before the cyclization reaction is often used, specifically a polyimide precursor or a polybenzo

The azole precursor is dissolved in a solvent. This makes it possible to achieve excellent workability, and when manufacturing each of the above-mentioned products, it can be applied to a substrate in various forms and processed. Thereafter, the cyclized polymer precursor can be heated to form a hardened product. In addition, when heating the cyclized polymer precursor, in order to prevent oxidation of the substrate, etc., the heating is performed in an atmosphere such as a nitrogen atmosphere with a reduced oxygen concentration.

唑前驅物中之樹脂膜在氮氣氛下進行熱處理之後，進而在包含氧之氣氛下進行熱處理之內容。 For example, Patent Document 1 describes forming a photosensitive polyimide resin layer by heating the photosensitive polyimide precursor layer at 200°C or more and 350°C or less in an environment with an oxygen concentration of 50 ppm or less. In addition, Patent Document 2 describes that a material selected from a photosensitive polyimide precursor or a photosensitive polybenzo

The resin film in the azole precursor is heat-treated in a nitrogen atmosphere and then heat-treated in an atmosphere containing oxygen.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2010-054451

[Patent Document 2] Japanese Patent Application Publication No. 2004-031564

唑前驅物等聚合物前驅物之樹脂組成物來製造硬化膜時，期望進一步降低加熱硬化溫度來進行。然而，隨著降低加熱硬化溫度，所獲得之硬化膜的延性等機械特性趨於降低。在專利文獻1、2中記載之發明中，亦難以製造滿足近年來要求水平之硬化膜。 Use polyimide precursors or polybenzo

When producing a cured film from a resin composition of a polymer precursor such as an azole precursor, it is desirable to further lower the heating and curing temperature. However, as the heat hardening temperature is lowered, mechanical properties such as ductility of the obtained cured film tend to decrease. Even in the inventions described in Patent Documents 1 and 2, it is difficult to produce a cured film that meets the level required in recent years.

Therefore, an object of the present invention is to provide a method for manufacturing a cured film, a method for manufacturing a resin composition, a cured film, a laminated body, and a method for manufacturing a semiconductor element that are excellent in mechanical properties.

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體之樹脂組成物，將使用該樹脂組成物來獲得之膜在氧分壓為6~150Pa的氣氛下加熱硬化， 能夠獲得機械特性優異之硬化膜，以至完成本發明。本發明提供以下內容。 According to the research of the present inventor, it was found that by using as a resin composition a polyimide precursor selected from the group consisting of polyimide precursors and polybenzo

A resin composition of at least one polymer precursor in the group of azole precursors and a radically polymerizable monomer, and the film obtained using the resin composition is heated and hardened in an atmosphere with an oxygen partial pressure of 6 to 150 Pa, A cured film excellent in mechanical properties can be obtained, leading to the completion of the present invention. The present invention provides the following.

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體之樹脂組成物適用於基板來形成膜之步驟；以及將膜在氧分壓為6~150Pa的氣氛下加熱硬化之步驟。 <1> A method for manufacturing a cured film, which includes: adding a polyimide precursor selected from the group consisting of a polyimide precursor and a polybenzo

The step of applying a resin composition of at least one polymer precursor in the group of azole precursors and a radically polymerizable monomer to a substrate to form a film; and heating and hardening the film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa. steps.

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

<3> The manufacturing method of the cured film according to <1> or <2>, wherein the film is heated to 170~350°C in the step of heating and hardening.

<4> The method for manufacturing a cured film according to any one of <1> to <3>, which includes a step of exposing the film and a step of exposing the film after the exposure between the step of forming the film and the step of heating and hardening. The film is developed.

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

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體，該樹脂組成物用於<1>~<6>中任一項所述之硬化膜的製 造方法。 <7>A resin composition comprising polyimide precursors and polybenzoyl

At least one polymer precursor and a radical polymerizable monomer in the group of azole precursors, and the resin composition is used in the method for manufacturing a cured film according to any one of <1> to <6>.

<8> A cured film obtained from the resin composition described in <7>.

<9> A method for manufacturing a laminated body, which includes the steps of forming a cured film by the method of manufacturing 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 manufacturing method of a semiconductor element, which includes the manufacturing method of the cured film according to any one of <1> to <6> or the manufacturing method of the laminated body according to <9>.

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

The contents of the present invention will be described below. In addition, in this specification, "~" is used to mean a range including the numerical values described before and after it as the lower limit and the upper limit.

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

Regarding the labels for groups (atomic groups) in this specification, labels that do not describe substituted or unsubstituted include both those without a substituent and those with a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

As long as "exposure" in this specification is not particularly limited, in addition to exposure using light, drawing using particle beams such as electron beams and ion beams is also included in the exposure. In addition, the light used for exposure generally includes active light or radiation such as far ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams, represented by the bright line spectrum of a mercury lamp and excimer laser.

In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid". Both or any one of them, "(meth)acrylyl group" means both or any one of "acrylyl group" and "methacrylyl group".

In this specification, the term "step" is not only an independent step, but also includes it in this term if it can achieve the expected effect of the step even if it is clearly distinguished from other steps.

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

In this 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 are defined as styrene-converted values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and as the column, a guard column HZ-L, TSKgel Super HZM-M, or TSKgel Super can be used. HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). In this measurement, unless otherwise specified, THF (tetrahydrofuran) was used as the eluent. Also, only Unless otherwise specified, detection is performed using a detector with a wavelength of UV rays (ultraviolet) of 254 nm.

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

[Manufacturing method of hardened film]

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體之樹脂組成物適用於基板來形成膜之步驟(膜形成步驟)和將上述膜在氧分壓為6~150Pa的氣氛下加熱硬化之步驟(加熱硬化步驟)。 The manufacturing method of the cured film of the present invention is characterized by comprising:

A resin composition of at least one polymer precursor in the group of azole precursors and a radically polymerizable monomer is applied to a substrate to form a film (film forming step) and the film is subjected to an oxygen partial pressure of 6 to 150 Pa The step of heating and hardening in an atmosphere (heating and hardening step).

According to the present invention, a cured film excellent in mechanical properties such as ductility can be formed. Although the detailed reason is not clear, it is presumed that by heating and curing the film in an atmosphere with a predetermined oxygen partial pressure, the amount of oxygen present increases and the original cross-linking density of the radically polymerizable monomer and the polymer precursor is slightly reduced. This is achieved by relaxing the interaction between the polymer precursors and increasing the resistance in the stress direction. In addition, it is generally considered that the polymerization reaction of radically polymerizable monomers is easily inhibited in the presence of oxygen. Therefore, it is thought that when a film obtained using a resin composition containing a radical polymerizable monomer is heated and cured, a cured film excellent in mechanical properties such as ductility can be obtained by lowering the oxygen partial pressure during heating and curing. However, surprisingly, by The film is heated and cured in an atmosphere with an oxygen partial pressure in the above range, and the mechanical properties such as ductility of the obtained cured film are improved.

In addition, since the oxygen partial pressure during heat curing is within the above range, oxidation of the substrate and the like can also be suppressed. Therefore, it is particularly effective when a substrate containing a metal layer or a metal substrate is used.

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

(a) The step of applying the resin composition to the substrate to form a film (film forming step), (b) The step of exposing the film after the film forming step (exposure step), (c) The exposed film The step of development (development step), (d) the step of heating and hardening the developed film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa (heating and hardening step).

Each step is explained in detail below.

<Film formation step>

唑前驅物之群組中之至少一種聚合物前驅物和自由基聚合性單體之樹脂組成物適用於基板而形成膜。關於樹脂組成物的詳細內容進行後述。 In the film forming step, a material selected from the group consisting of polyimide precursors and polybenzoyl

A resin composition of at least one polymer precursor from the group of azole precursors and a radically polymerizable monomer is applied to a substrate to form a film. Details of the resin composition will be described later.

唑、聚苯硫醚、聚環烯烴、降莰烯樹脂、聚氯三氟乙烯等氟樹脂、液晶聚合物、丙烯酸樹脂、環氧樹脂、矽酮樹脂、離子聚合物樹脂、氰酸鹽樹脂、交聯反丁烯二酸二酯、環狀聚烯烴、芳香族醚、順丁烯醯亞胺、烯烴、纖維素、環硫化合物等的合成樹脂之基板。在樹脂基板的表面可形成有金屬層。本發明中，在使用具有金屬層之基板或金屬基板時，亦能夠形成抑制金屬的氧化等並且延性等機械特性優異之硬化膜，因此使用該種基板時，尤其有效。 The type of substrate can be appropriately determined depending on the use. Examples include inorganic substrates, resin substrates, resin composite material substrates, and the like. Examples of inorganic substrates include silicon substrates, silicon nitride substrates, polycrystalline silicon substrates, silicon oxide substrates, amorphous silicon substrates, glass substrates, quartz substrates, metal substrates, and the like. Metal layers of molybdenum, titanium, aluminum, copper, etc. may be formed on the surfaces of silicon substrates, silicon nitride substrates, polycrystalline silicon substrates, silicon oxide substrates, amorphous silicon substrates, glass substrates, and quartz substrates. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, poly Polyamide, polyether ester, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imine, polyether imine, polybenzo

Azole, polyphenylene sulfide, polycyclic olefin, norbornene resin, polychlorotrifluoroethylene and other fluororesins, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, Substrate for synthetic resins such as cross-linked fumarate diester, cyclic polyolefin, aromatic ether, maleimide, olefin, cellulose, episulfide compound, etc. A metal layer may be formed on the surface of the resin substrate. In the present invention, even when a substrate having a metal layer or a metal substrate is used, it is possible to form a cured film that suppresses oxidation of metal and has excellent mechanical properties such as ductility. Therefore, it is particularly effective when using such a substrate.

As a method of applying the resin composition to the substrate, coating is preferred. Specifically, examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the formed film (resin composition layer), spin coating, slit coating, spray coating, and inkjet are more preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a film (resin composition layer) with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferable. If it is a rectangular substrate, slit coating is preferable. Or spraying method, inkjet method, etc. are better. In the case of the spin coating method, for example, coating can be performed at a rotation speed of 500 to 2000 rpm and 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°C, more preferably 70 to 130°C, and further preferably 90 to 110°C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and even more preferably 3 to 7 minutes.

<Exposure steps>

The film manufacturing method of the present invention may include a step of exposing the film (exposure step) after the film forming step. In the exposure step, a stepper exposure machine, a scanning exposure machine, or the like is used to expose the film (resin composition layer) through a mask having a predetermined mask pattern, whereby the film (resin composition layer) can be exposed in a pattern.

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

<Development step>

The film manufacturing method of the present invention may include a step of developing the exposed film (resin composition layer) (development step). By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as spin immersion, spray, immersion, and ultrasonic waves can be used.

Development is performed using a developer. The developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion). It is preferred that the developer contains an organic solvent, and it is even more preferred that the developer contains more than 90% organic solvent. In the present invention, it is preferable that the developer contains an organic solvent with a ClogP value of -1 to 5, and it is even more preferable that the developer contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula into ChemBioDraw.

Regarding the organic solvent, suitable examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate esters, etc.)), 3-alkoxypropionic acid alkyl esters (for example: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester) Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate ester)), 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, 2-oxobutanate acid methyl ester, ethyl 2-oxobutyrate, etc., and as ethers, suitable examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl ether. Cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, suitable examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3- Heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. can be suitably mentioned, and as teresine, suitable examples can be given Out of dimethyl sulfoxide.

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

It is preferable that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and still more preferably 90% by mass or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but it can usually be performed at 20 to 40°C.

After treatment with developer, rinse can be carried out. It is better to use a different solvent from the developer for rinsing. For example, the solvent contained in the resin composition may be used for flushing. The optimal flushing time is 5 seconds to 1 minute.

<Heat hardening step>

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

In the present invention, the above film is heated in an atmosphere with an oxygen partial pressure of 6 to 150 Pa. The upper limit of the oxygen partial pressure in the heating step is preferably 120 Pa or less, more preferably 100 Pa or less, and further preferably 60 Pa or less, in order to suppress corrosion of the substrate. In addition, the lower limit of the oxygen partial pressure is preferably 7 Pa or more, more preferably 10 Pa or more, and further preferably 30 Pa or more, since it is easier to obtain a cured film having better mechanical properties such as ductility. In addition, when the film is heated in the heating chamber, the oxygen partial pressure in the heating chamber is equivalent to the oxygen partial pressure in the atmosphere of the heating and hardening step.

Examples of methods for adjusting the oxygen partial pressure in the atmosphere in the heating and hardening step to the above range include a method of adjusting the oxygen partial pressure by replacing the gas in the atmosphere in the heating chamber with an inert gas, and depressurizing the heating chamber. As for the method of adjusting the oxygen partial pressure, for the reason of membrane stability, a method of replacing the gas in the atmosphere in the heating chamber with an inactive gas and adjusting the oxygen partial pressure is preferable. Examples of the inert gas include nitrogen, helium, argon, and the like.

From the viewpoint of film stability, the atmospheric pressure in the heating and hardening step is preferably 0.08 to 0.12MPa, and more preferably 0.09 to 0.11MPa. Furthermore, when the film is heated in the heating chamber, the pressure in the heating chamber is equivalent to the atmospheric pressure in the heating and hardening step.

In addition, the oxygen concentration in the atmosphere of the heat hardening step is preferably greater than 60 volume ppm and 1500 volume ppm or less. The lower limit is preferably 65 ppm by volume or more, and 100 The volume ppm or more is more preferable, and the volume ppm or more is further more preferable. The upper limit is preferably 1,400 volume ppm or less, more preferably 1,200 volume ppm or less, and still more preferably 1,000 volume ppm or less. In addition, when the film is heated in the heating chamber, the oxygen concentration in the heating chamber is equivalent to the oxygen concentration in the atmosphere of the heating and hardening step.

The heating temperature (maximum heating temperature) of the film in the heat-hardening step is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, 150°C or higher still more preferably, and 160°C or higher. It is further more preferable, and it is still more preferable that it is 170 degreeC or more. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, further preferably 350°C or lower, further preferably 250°C or lower, and still further preferably 220°C or lower. In addition, the heating temperature (maximum heating temperature) of the film is preferably 170 to 350°C.

Regarding heating, it is preferable to conduct the heating at a temperature rising rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature rise rate to 1°C/min or more, excessive volatilization of amine can be prevented while ensuring productivity, and by setting the temperature rise rate to 12°C/min or less, the residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and still more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at which the step of heating to the maximum heating temperature begins. For example, when the resin composition is applied to the substrate and then dried, the temperature of the dried film (layer) is, for example, from a temperature that is 30 to 200°C lower than the boiling point of the solvent contained in the resin composition. Warming up is better.

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

Especially when forming a multilayer laminate, from the viewpoint of interlayer adhesion of the cured film, the film is preferably heated at 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is not certain, but it is considered that the reason is that by setting this temperature, the ethynyl groups of the polymer precursor between the layers undergo a cross-linking reaction.

Heating can be done in stages. As an example, the temperature can be increased from 25°C to 180°C at 3°C/min and held at 180°C for 60 minutes, and the temperature can be raised from 180°C to 200°C at 2°C/min and held at 200°C for 120 minutes. steps. As a pretreatment step, the heating temperature is preferably 100~200°C, more preferably 110~190°C, and further preferably 120~185°C. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the membrane can be improved through these pre-treatment steps. The pretreatment step can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be more than two stages. For example, pretreatment step 1 can be performed in the range of 100 to 150°C, and then pretreatment step 2 can be performed in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5° C./minute.

A cured film can be produced through the above steps. Examples of fields to which the cured film can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), or etching for actual mounting purposes such as the above can be cited. The insulating film is patterned, etc. Regarding such uses, for example, you can refer to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials" "Basic and Development" released in November 2011, Japan Polyimide. Aromatic Polymer Research Society/edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc. Furthermore, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, use of molded parts, production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

[Method for manufacturing laminated body]

The manufacturing method of a laminated body of this invention includes the step of forming a cured film by the manufacturing method of the cured film of this invention (cured film forming step), and the step of forming a metal layer on the surface of this cured film (metal layer forming step).

The type of metal layer formed on the surface of the cured film is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred. , copper is further preferred. The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application 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, and methods combining these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited. The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest wall thickness. 1~10μm is better.

In the manufacturing method of the laminated body of the present invention, it is also preferable to form a cured film on the surface of the cured film (resin layer) or the metal layer again by the above-mentioned manufacturing method of the cured film of the present invention after the metal layer forming step.

Moreover, the manufacturing method of the laminated body of this invention can alternately perform the cured film formation step and the metal layer formation step a plurality of times (preferably 2 to 7 times, more preferably 2 to 5 times). In this manner, a laminated body having a multilayer wiring structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer can be produced by alternately stacking a plurality of cured films (resin layers) and metal layers.

[Manufacturing method of semiconductor elements]

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

[Resin composition]

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

<Polymer precursor>

唑前驅物中之聚合物前驅物。從容易更顯著獲得本發明的效果的理由考慮，本發明中使用的聚合物前驅物係聚醯亞胺前驅物為較佳。 The resin composition of the present invention contains polyimide precursors and polybenzoyl

Polymer precursor in azole precursor. The polymer precursor used in the present invention is preferably a polyimide precursor because the effect of the present invention can be more easily obtained.

<<Polyimide precursor>>

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

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

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

<<<R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group containing a combination thereof, and a linear aliphatic group having 2 to 20 carbon atoms. Preferably, a group including a family group, a branched chain 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 combination thereof, and carbon Aromatic groups with a number of 6 to 20 are more preferred.

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

Specifically, the diamine includes a linear aliphatic group with 2 to 20 carbon atoms, a branched or cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group containing these combinations. Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. as Examples of the aromatic group include the following aromatic groups.

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

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-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl cyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenyl sulfide and 3,3-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide Ether and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl- 4,4'-Diaminobiphenyl, 2,2'-Dimethyl-4,4'-Diaminobiphenyl (4,4'-Diamino-2,2-dimethylbiphenyl) , 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) Hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis( 3-Amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)propane, bis (4-Amino-3-hydroxyphenyl)terine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4 -Aminophenoxy)phenyl]terine, bis[4-(3-aminophenoxy)phenyl]terine, bis[4-(2-aminophenoxy)phenyl]terine, 1, 4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone , 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3, 3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminobiphenyl Phenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4- Aminophenyl)fluoride, 4,4'-dimethyl-3,3'-diaminodiphenyltrifluoride, 3,3',5,5'-tetramethyl-4,4'-diamine diphenylmethane, 2-(3',5'-diaminobenzyloxy)ethyl 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-diaminofluoride, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, Diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4- Aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropentane Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis Methylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4- Amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amine methyl-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsine, 4,4'-bis(3 -Amino-5-trifluoromethylphenoxy)diphenyltrine, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2 , at least one diamine among 2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

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

[Chemical 3]

Furthermore, as a preferred example, a diamine having at least two alkylene glycol units in the main chain can also be cited. Preferably, a diamine containing two or more ethylene glycol chains, propylene glycol chains, or both is combined in one molecule, and more preferably, a diamine does not contain an aromatic ring. Specific examples 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), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1- (2-aminopropoxy)propan-2-yl)oxy)propan-2-amine and the like, but are not limited to these.

The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) Registered Trademark) Structure of EDR-176.

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

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

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

R ⁵⁰ ~ R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ ~ R ⁵⁷ is a fluorine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl .

Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Fluorinated alkyl groups (numbers 1 to 6), etc.

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

Examples of the diamine compound that provides the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl and 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One type of these may be used, or two or more types may be used in combination.

<<<R ¹¹⁵ >>>

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

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

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

R ¹¹⁵ represents a tetravalent organic group. The definition of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 ,2-Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3, 3'-Diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8- Naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3, 4-Dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and their alkyl derivatives with 1 to 6 carbon atoms and alkoxy groups with 1 to 6 carbon atoms At least one of the derivatives.

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

<<<R ¹¹³ and R ¹¹⁴ >>>

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

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

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, carbon Numbers 1 to 12 are better, 1 to 6 are better, and 1 to 3 are particularly good; repeat numbers of 1 to 12 are better, 1 to 6 are better, and 1 to 3 are particularly good). Furthermore, the (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecylmethylene, -CH ₂ CH(OH)CH ₂ -, ethylidene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ - are Better.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethyl group.

As a preferred embodiment of the polyimide precursor in the present invention, examples of the monovalent organic group of R ¹¹³ or R ¹¹⁴ include 1, 2 or 3 acid groups, preferably one acid group. Aliphatic groups, aromatic groups and aralkyl groups, etc. Specific examples include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acid group is preferably a hydroxyl group. That is, it is preferable that R ¹¹³ or R ¹¹⁴ is a group having a hydroxyl group.

As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developer can preferably be used.

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

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

The number of carbon atoms in the alkyl group is preferably 1 to 30 (when it is cyclic, it is 3 or more). The alkyl group may be linear, branched, or cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Alkyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Dihydryl, dicyclohexyl and pinenyl. Furthermore, as the alkyl group substituted by an aromatic group, a linear alkyl group substituted by an aromatic group described below is preferred.

環、三伸苯環等)或經取代或未經取代的芳香族雜環基(作為構成基團之環狀結構，茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、

唑環、噻唑環、吡啶環、吡

環、嘧啶環、噠

環、吲哚

環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹

環、喹啉環、酞

環、萘啶環、喹

啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、

環、啡

噻環、啡噻

環或啡

環)。 The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes benzene ring, naphthalene ring, biphenyl ring, fluorine ring, pentene ring, Indene ring, azulene ring, heptacene ring, indene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

ring, triphenyl ring, etc.) or substituted or unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, fluorine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyridine ring, pyridine ring

ring, pyrimidine ring, da

ring, indole

ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinine

ring, quinoline ring, phthalein

ring, naphthyridine ring, quinine

Phenoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring,

ring, coffee

thiocycline, thiophene

ring or brown

ring).

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

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

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

[Chemical 11]

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, among R ¹¹³ and R ¹¹⁴ It is preferred that at least one of the groups contains a radically polymerizable group, and a radically polymerizable group is more preferred.

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

The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), among which oxygen atom is more preferred.

In the formula (1-A), the bonding position of the carbonyl group on the benzene ring is preferably 4, 5, 3’, or 4’. In formula (1-B), 1, 2, 4, and 5 are preferred.

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

As an embodiment of the polyimide precursor in the present invention, it may be 50 mol% or more of the total structural units, further 70 mol% or more, especially 90 mol%. % or more are polyimide precursors having structural units represented by formula (1). As an upper limit, it is actually 100 mol% or less.

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

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

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

In the method for producing the polyimide precursor, it is preferable to use an organic solvent when carrying out the reaction. The number of organic solvents may be one type, or two or more types.

The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diglyme, N-methylpyrrolidone, and N-ethylpyrrolidone.

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

唑前驅物>> <<polybenzo

Azole precursor>>

唑前驅物包含由下述式(2)表示之構成單元為較佳。 polybenzo

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

[Chemical 12]

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

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is particularly preferred) and aromatic group (carbon number 6 to 22 is preferred, 6 is preferred) ~14 is more preferred, 6~12 is particularly preferred) at least one group is preferred. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ of the above formula (1). As the above-mentioned aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxobenzoyl chloride.

In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. The definitions are the same as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

唑前驅物還可以包含其他種類的構成單元。 In addition to the structural units of the above-mentioned formula (2), polybenzo

Azole precursors may also contain other types of building blocks.

唑前驅物包含由下述式(SL)表示之二胺殘基來作為其他種類的構成單元為較佳。 From the viewpoint of being able to suppress the occurrence of warpage of the cured film accompanying loop closure, polybenzo

The azole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit.

[Chemical 13]

Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 10 (preferably a carbon number of 1 to 6, more preferably a carbon number of 1 to 3), R ^2s is a carbon number of 1 to 10 Hydrocarbon group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably having 6 to 22 carbon atoms, More preferably, it has a carbon number of 6 to 18, particularly preferably a carbon number of 6 to 10), and the remaining part is a hydrogen atom or a carbon number of 1 to 30 (more preferably, a carbon number of 1 to 18, more preferably a carbon number of 1 to 12, especially Preferably, they are organic groups having 1 to 6 carbon atoms, and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, it is preferable that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

唑前驅物的脫水閉環後的彈性率，且抑制翹曲之效果和提高溶解性之效果。 In the formula (SL), preferred examples of Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the above molecular weight to the above range, it is possible to simultaneously reduce the polybenzo

The elastic modulus of the azole precursor after dehydration and ring closure, and the effect of inhibiting warpage and improving the solubility.

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it also contains the tetracarboxylic acid dianhydride group remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride in order to improve the alkali solubility. Acid residues are preferred as structural units. Examples of these tetracarboxylic acid residues include R ¹¹⁵ in formula (1).

唑前驅物的重量平均分子量(Mw)較佳為2000~500000，更佳為5000~100000，進一步較佳為10000~50000。又，數平均分子量(Mn)較佳為800~250000，更佳為2000~50000，進一步較佳為4000~25000。 polybenzo

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

唑前驅物的分子量的分散度為1.5~3.5為較佳，2~3為更佳。 polybenzo

The molecular weight dispersion of the azole 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 mass% or more relative to the total solid content of the resin composition, more preferably 30 mass% or more, further preferably 40 mass% or more, and 50 mass% % or more is more preferably, 60 mass % or more is still more preferably, and 70 mass % or more is still more preferably. Furthermore, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5 mass% or less, more preferably 99 mass% or less, and further preferably 98 mass% or less relative to the total solid content of the resin composition. 95 mass % or less is further more preferable.

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

<Radically polymerizable monomer>

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

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

The molecular weight of the radically polymerizable monomer is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable monomer is preferably 100 or more.

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

Specific examples of radically polymerizable monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides. The compounds are preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reaction products of unsaturated carboxylic esters or amides having affinity substituents such as hydroxyl groups, amine groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups, monofunctional or polyfunctional alcohols, amines, Addition reactants of thiols and substitution of unsaturated carboxylic acid esters or amides with releasable substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols Reactants are also preferred. As another example, instead of the unsaturated carboxylic acid, a group of compounds substituted by unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, and these contents are incorporated into this specification.

Furthermore, a compound in which the radically polymerizable monomer has a boiling point of 100° C. or higher under normal pressure is also preferred. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopenterythritol triacrylate. (Meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, hexanediol (meth)acrylate acrylate, trimethylolpropane tris(acrylyloxypropyl) ether, tris(acrylyloxyethyl)isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohols Compounds that are (meth)acrylated after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193 (Meth)acrylic urethanes described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, polyester acrylates, Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are the reaction products of epoxy resin and (meth)acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Furthermore, 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 and the like can also be cited.

In addition, as preferred radical polymerizable monomers other than the above, monomers having a fluorine ring described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. can also be used. , and a compound or cardo resin having two or more groups containing ethylenically unsaturated bonds.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Publication No. 02-040336 can also be cited. Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Application Publication No. Sho 61-022048 can also be used. Furthermore, those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

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

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

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 into this specification.

As the radical polymerizable monomer, dipenterythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol tetraacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipenterythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin- Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acrylyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. These oligomer types can also be used.

Examples of commercially available radical polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethoxyl chains, and SR-494, a tetrafunctional acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc. SR-209, 231, 239 manufactured by Sartomer Company, Inc., a bifunctional methyl acrylate, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., and DPCA-60, a hexafunctional acrylate having 3 TPA-330, a trifunctional acrylate with an isobutoxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION.) ), M-306 (manufactured by TOAGOSEI CO., Ltd.), etc.

Examples of radically polymerizable monomers include those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Urethane acrylates, epoxy resins described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Urethane compounds with an ethane-based skeleton are also preferred. Furthermore, as the radical polymerizable monomer, monomers having an amine group in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 01-105238 can also be used. Structure or sulfide structure of compounds.

The radically polymerizable monomer may be a compound having an acid group such as a carboxyl group or a phosphate group. Among radically polymerizable monomers having acidic groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The unreacted hydroxyl groups of the aliphatic polyhydroxy compounds react with non-aromatic carboxylic acid anhydrides to obtain acidic groups. compounds are better. Particularly preferred are compounds having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The aliphatic polyhydroxy compound is a compound of neopentylerythritol and/or dineopenterythritol. As commercially available products, for example, polybasic acid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510, M-520, and the like.

The preferred acid value of radically polymerizable monomers with acidic groups is 0.1 to 40 mgKOH/g, especially 5~30 mgKOH/g. As long as the acid value of the radically polymerizable monomer is within the above range, the production and workability will be excellent, and the developability will be excellent. In addition, the polymerizability is also good.

From the viewpoint of suppressing warpage associated with control of the elastic modulus of the cured film, a monofunctional radical polymerizable monomer can be suitably used as the radical polymerizable monomer in the resin composition of the present invention. As the monofunctional radical polymerizable monomer, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butyl(meth)acrylate can be preferably used. Oxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate , N-hydroxymethyl (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, trimellitic acid triene Allyl compounds such as propyl ester, etc. As the monofunctional radical polymerizable monomer, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred.

The content of the radically polymerizable monomer is preferably 1 to 60% by mass relative to the total solid content of the resin composition of the present invention. It is more preferable that the lower limit is 5 mass % or more. It is more preferable that the upper limit is 50 mass % or less, and it is further more preferable that it is 30 mass % or less. A radically polymerizable monomer may be used individually by 1 type, and may be used in mixture of 2 or more types. When two or more types are used at the same time, the total amount is preferably within the above range.

<Other polymeric compounds>

化合物。 The resin composition of the present invention may further contain polymerizable compounds (hereinafter also referred to as other polymerizable compounds) other than the radically polymerizable monomers. Examples of other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or a hydroxymethyl group; epoxy compounds; oxetane compounds; and benzo compounds.

compound.

<<Compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl>>

As the compound having a hydroxymethyl group, an alkoxymethyl group or a carboxyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

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

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

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

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

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

<<Epoxy compounds (compounds with epoxy groups)>>

As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy performs cross-linking reaction below 200℃ and does not cause It is difficult to cause film shrinkage due to the dehydration reaction of cross-linking. Therefore, by containing an epoxy compound, low-temperature hardening and warpage of the composition can be effectively suppressed.

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

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

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

Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzene dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone, or both of them can be mixed. More than one species.

化合物(具有聚苯并

唑基之化合物)>> <<Benzo

Compounds (with polybenzo

Azole-based compounds)>>

化合物因源自開環加成反應之交聯反應而於硬化時不產生脫氣，進而減少熱收縮而抑制產生翹曲，因此為較佳。 Benzo

The compound is preferable because it does not produce outgassing during hardening due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and suppressing warpage.

化合物的較佳例子，可舉出B-a型苯并

、B-m型苯并

(Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并

加成物、酚醛清漆型二氫苯并

化合物。該等可以單獨使用，或者可以混合兩種以上。 as benzo

Preferable examples of the compound include Ba-type benzo

, Bm type benzo

(manufactured by Shikoku Chemicals Corporation), polyhydroxystyrene resin benzo

Adduct, novolak type dihydrobenzo

compound. These may be used alone, or two or more types may be mixed.

When other polymerizable compounds are contained, their content is preferably greater than 0% by mass and not more than 60% by mass relative to the total solid content of the resin composition of the present invention. It is more preferable that the lower limit is 5 mass % or more. It is more preferable that the upper limit is 50 mass % or less, and it is further more preferable that it is 30 mass % or less. One type of other polymerizable compounds may be used alone, or two or more types may be mixed and used. When two or more are used at the same time, the total amount becomes the above The range is better.

<Thermal base generator>

The resin composition of the present invention preferably contains a thermal base generator. The thermal base generator is not particularly limited in type, etc., but contains at least one selected from the group consisting of acidic compounds that generate bases when heated to 40° C. or above, and ammonium salts having pKa1 of 0 to 4 anions and ammonium cations. Base generators are preferred. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later.

By blending these compounds, a cyclization reaction of a polymer precursor or the like can be performed at low temperature. In addition, the thermal base generator does not generate a base without heating. Therefore, even if it coexists with the polymer precursor, it can suppress cyclization of the polymer precursor during storage and has excellent storage stability.

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

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

The base generated by a hot base generator is a secondary amine or a tertiary amine, and a tertiary amine is more preferred. Tertiary amines are highly basic and therefore enable lower cyclization temperatures of the polymer precursor. In addition, the boiling point of the base generated by the thermal base generator is preferably 80°C or higher, more preferably 100°C or higher, and further preferably 140°C or higher. In addition, the molecular weight of the produced base is preferably 80 to 2000. It is better if the lower limit is 100 or more. It is better if the upper limit is less than 500. In addition, the value of molecular weight is a theoretical value calculated from the structural formula.

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

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

In this embodiment, the ammonium salt represents a salt of an ammonium cation and anion represented by the following formula (101) or formula (102). The anion can be bonded to any part of the ammonium cation via covalent bonding, or it can exist outside the molecule of the ammonium cation, but there are It is better to be outside the molecule of ammonium cation. In addition, the presence of an anion outside the molecule of an ammonium cation means that the ammonium cation and the anion are bonded without covalent bonding. Hereinafter, the extramolecular anion in the cation part is also called a counter anion.

Formula (101) Formula (102)

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

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

In the formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and the meanings of R ¹ and R ⁷ are the same as those of the formula (101) or the formula (102).

In the formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

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

The type of anion is preferably one selected from the group consisting of carboxylate anions, phenol anions, phosphate anions and sulfate anions, and carboxylate anions are more preferred from the viewpoint of balancing the stability and thermal decomposition properties of the salt. That is, the ammonium salt is more preferably a salt of ammonium cation and carboxylate anion.

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

In this embodiment, the carboxylate anion system is an anion of carboxylic acid with pKa1 of 4 or less. Son is better. It is more preferable that pKa1 is 3.5 or less, and it is further more preferable that it is 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.

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

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

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

In this embodiment, the electron-withdrawing group represents a Hammett substituent constant σm that represents a positive value. Among them, σm is explained in detail in Mr. Yuhio Tsuno, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in this embodiment is not limited to the substituent described in the above-mentioned document.

Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (σm=0.21), and CH ₂ =CH group (σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06) wait. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

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

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

In this embodiment, the carboxylate anion is preferably represented by the following formula (XA).

In the formula (XA), L ¹⁰ represents a divalent connecting group selected from a single bond or an alkylene group, ^an alkenylene group, an aromatic group, ^-NR base, alkenyl or aryl group.

Specific examples of carboxylate anions include maleate anions, phthalate anions, N-phenyliminodiacetate anions, and oxalate anions. Can better use these.

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

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

<Radical polymerization initiator>

The resin composition of the present invention preferably contains a radical polymerization initiator. Especially when using a polymer precursor containing a radically polymerizable group or using a self-containing polymer precursor In the case of a radical polymerizable compound, the resin composition of the present invention preferably contains a radical polymerization initiator. Examples of radical polymerization initiators include photo radical polymerization initiators and thermal radical polymerization initiators. The radical polymerization initiator used in the resin composition of the present invention is preferably a photo-radical polymerization initiator.

<<Photoradical polymerization initiator>>

The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light from an ultraviolet region to a visible region is preferred. In addition, it can be an active agent that interacts with the sensitizer excited by light and generates active free radicals.

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

骨架之化合物、具有

二唑骨架之化合物、具有三鹵甲基之化合物等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等的詳細內容，能夠參閱日本特 開2016-027357號公報的0165~0182、國際公開第2015/199219號的0138~0151段的記載，該內容編入本說明書中。 As the photoradical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (for example, having three

A compound with a skeleton

Compounds with an oxadiazole skeleton, compounds with trihalomethyl groups, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, Aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, etc. For details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and these contents are incorporated into this specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, and this content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can be preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

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

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

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

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, 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) and the like.

As a photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, the exposure latitude can be further effectively increased. Among oxime compounds, they are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photohardening accelerator.

As specific examples of the oxime compound, compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166 can be used.

Preferred oxime compounds include, for example, compounds with the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyiminobutan-1-phenylpropane-1- ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Application Publication No. 2012-014052 Photoradical polymerization initiator 2) described in the Gazette No. Moreover, TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

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

Preferred oxime compounds include oxime compounds having specific substituents shown in Japanese Patent Application Laid-Open No. 2007-269779 or oxime compounds having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. Compounds etc.

化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基

二唑化合物、3-芳基取代香豆素化合物之群 組中之化合物。 From the perspective of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyltri

Compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds , benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl

Compounds in the group of oxadiazole compounds and 3-aryl substituted coumarin compounds.

化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物，選自包括三鹵甲基三

化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中之至少一種化合物為進一步較佳，使用茂金屬化合物或肟化合物為更進一步較佳，肟化合物為更進一步較佳。 A better photoradical polymerization initiator is trihalomethyltri

Compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, selected from the group consisting of Trihalomethyltri

It is further preferred to use at least one compound from the group consisting of a compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound, and it is further preferred to use a metallocene compound or an oxime compound, Oxime compounds are further preferred.

啉基苯基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-

啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環進行縮環而成之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又，還能夠使用由下述式(I)表示之化合物。 In addition, as the photoradical polymerization initiator, N benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-

Phyllinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-

Aromatic ketones such as pholinyl-acetone-1, alkyl anthraquinones and other quinones formed by ring condensation with aromatic rings, benzoin ether compounds such as benzoin alkyl ether, benzoin, alkyl benzoin and other benzoin compounds, benzyl dimethyl Benzyl derivatives such as ketals, etc. Moreover, the compound represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group. Alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, halogen atoms, cyclopentyl groups, cyclohexyl groups, and alkenyl groups with 2 to 12 carbon atoms are interrupted by one or more oxygen atoms. At least one substituted phenyl or biphenyl group among the alkyl groups having 2 to 18 carbon atoms and the alkyl groups having 1 to 4 carbon atoms, R ^I01 is a group represented by formula (II), or the same group as R ^I00 , R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

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

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

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

<<Thermal radical polymerization initiator>>

Thermal radical polymerization initiator is a compound that generates free radicals by heat energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymer precursor can be cyclized and the polymerization reaction of the polymer precursor can proceed. Therefore, a higher degree of heat resistance can be achieved. as thermal radical Specific examples of the 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, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % relative to the total solid content of the resin composition of the present invention. Mass %. Thermal radical polymerization initiator may contain only one type or two or more types. When two or more thermal radical polymerization initiators are contained, the total amount is preferably within the above range.

<Solvent>

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

Examples of preferred esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, Alkoxyethyl acetate, alkoxybutyl acetate (e.g., methyl methoxyacetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-Methoxypropyl propionate, 2-ethoxy Methyl propionate, 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, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetic acid Methyl ester, ethyl acetyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

Examples of preferred ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropylene Ether acetate, etc.

Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like.

Preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.

Preferable examples of the sericene include dimethyl serotonin.

Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, etc.

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the properties of the coating surface.

In the present invention, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. , methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, ethanol One solvent or a mixture of two or more of carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidinone, propylene glycol methyl ether and propylene glycol methyl ether acetate. Solvent is preferred. It is particularly good to use dimethylsulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the resin composition of the present invention is preferably 5 to 80 mass %, and is more preferably 5 to 75 mass %. Preferably, the amount is 10 to 70 mass %, which is still more preferable, and the amount of 40 to 70 mass % is still more preferable. The content of the solvent can be adjusted according to the desired thickness and coating method.

The solvent may contain only one type or two or more types. When two or more solvents are contained, the total amount is preferably within the above range.

<Migration inhibitor>

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

唑環、噻唑環、吡唑環、異

唑環、異噻唑環、四唑環、吡啶環、嗒

環、嘧啶環、吡

環、哌啶環、哌嗪環、

啉環、2H-吡喃環及6H-吡喃環、三

環)之化合物、具有硫脲類及氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。 The migration inhibitor is not particularly limited, and examples thereof include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring,

Azole ring, thiazole ring, pyrazole ring, iso

Azole ring, isothiazole ring, tetrazole ring, pyridine ring,

ring, pyrimidine ring, pyridine

ring, piperidine ring, piperazine ring,

Phenyl ring, 2H-pyran ring and 6H-pyran ring, three

ring), compounds with thiourea and hydrogen sulfide groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be suitably used.

In addition, an ion scavenger that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and the compounds described in Japanese Patent Application Laid-Open No. 2011-059656 can be used. Compounds described in Paragraph 0052 of Japanese Patent Application Publication No. 2012-194520, compounds described in Paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, compounds described in Paragraph 0166 of International Publication No. 2015/199219, etc.

Specific examples of the migration inhibitor include the following compounds.

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

<Polymerization inhibitor>

、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-第三丁基-4-甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺基丙基胺)苯酚、N-亞硝基-N-(1-萘基)羥胺銨鹽、雙(4-羥基-3,5-第三丁基)苯基甲烷等。又，亦能夠使用日本特開2015-127817號公報的0060段中記載之聚合抑制劑及國際公開第2015/125469號的0031~0046段中記載之化合物。又，還能夠使用下述化合物(Me為甲基)。 The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1 ,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl (6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, thiophene

, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-diaminetetraacetic acid 3-Butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso -5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiary butylamine) base) phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. Furthermore, the following compounds (Me is methyl) can also be used.

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

<Metal adhesion improver>

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

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

Moreover, as the metal adhesion improving agent, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also 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 further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the polymer precursor. By setting it above the above lower limit value, the hardening step The adhesiveness between the cured film and the metal layer after the step becomes good, and by setting it below the above upper limit, the heat resistance and mechanical properties of the cured film after the hardening step become good. The number of metal adhesion improvers may be only one type, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<Other additives>

The resin composition of the present invention can contain various additives as necessary, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic Particles, hardener, hardening catalyst, filler, antioxidant, ultraviolet absorber, aggregation inhibitor, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<<Thermal acid generator>>

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

The content of the thermal acid generator is preferably 0.01 parts by mass or more based on 100 parts by mass of the polymer precursor, and more preferably 0.1 parts by mass or more. Containing 0.01 parts by mass or more of the thermal acid generator accelerates the cross-linking reaction and cyclization of the polymer precursor, thereby further improving the mechanical properties and chemical resistance of the cured film. Moreover, from the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.

Only one type of thermal acid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<<sensitizing pigment>>

The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and enters an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with the thermal hardening accelerator, thermal radical polymerization initiator, photo radical polymerization initiator, etc., resulting in electron transfer, energy transfer, heat generation and other effects. Thereby, the thermal hardening accelerator, thermal radical polymerization initiator, and photo radical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and this content is incorporated into this specification.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and 0.5 to 0.5 mass %. 10% by mass is further more preferable. One type of sensitizing dye may be used alone, or two or more types of sensitizing dyes may be used simultaneously.

<<Chain transfer agent>>

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

In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used as the chain transfer agent.

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

<<Surfactant>>

From the viewpoint of further improving coatability, various surfactants may be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferred.

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

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

<<Higher fatty acid derivatives>>

In order to prevent polymerization inhibition due to oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention to be locally present in the composition during the drying process after coating. s surface.

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

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The number of higher fatty acid derivatives may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total range is preferably within the above range.

<Restrictions on other contained substances>

From the viewpoint of the properties of the coated surface, 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 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 further preferably less than 0.5 mass ppm. good. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total amount of these metals is preferably within the above range.

Furthermore, as a method of reducing metal impurities unintentionally contained in the resin composition of the present invention, the selection of metals as raw materials constituting the resin composition of the present invention can be cited. For raw materials with a small content, the raw materials constituting the resin composition of the present invention are filtered, the inside of the device is lined with polytetrafluoroethylene, and distillation is performed under conditions that suppress pollution as much as possible.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. Better still. Among them, the amount of halogen ions present in the state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total number of chlorine atoms and bromine atoms or chlorine ions and bromide ions is within the above range.

As a container for storing the resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into raw materials or compositions, it is also preferable to use a multi-layer bottle with an inner wall of six types of six-layer resins or a bottle with six types of resins formed into a seven-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

[Preparation of resin composition]

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

In addition, for the purpose of removing foreign matter such as garbage and particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be pre-cleaned with organic solvents. pass In the filtration step of the filter, multiple types of filters can be used in parallel or in series. When using multiple types of filters, filters with different pore sizes or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, cyclic filtering can be used. Alternatively, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

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

[hardened film]

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

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

The cured film of the present invention can be laminated in two or more layers and further in 3 to 7 layers to form a laminated body. The laminate system having two or more layers of the cured film of the present invention is preferably one in which a metal layer is provided between the cured films. These metal layers can be preferably used as metal wiring such as rewiring layers.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, layers inter-insulating film) or when the insulating film for actual mounting purposes is patterned by etching. Regarding such uses, for example, you can refer to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials" "Basic and Development" released in November 2011, Japan Polyimide. Aromatic Polymer Research Society/edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

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

[Example]

Hereinafter, the present invention will be described in further detail with reference to examples. The materials, usage amounts, proportions, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Examples and Comparative Examples>

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

[Table 1]

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

(polymer precursor)

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

唑前驅物(Mw=25000)

A-2: Polybenzo with the following structure

Azole precursor (Mw=25000)

(starter)

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

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

B-3: IRGACURE 784 (made by BASF)

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

(polymerizable monomer)

C-1: SR-209 (made by Arkema Corporation)

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

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

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

(solvent)

D-1: N-methylpyrrolidone

D-2: Ethyl lactate

D-3: γ-butyrolactone

D-4: dimethyl sulfoxide

(heat base generator)

E-1: The following compound

E-2: The following compounds

E-3: The following compounds

E-4: The following compounds

(silane coupling agent)

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

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

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

[Chemical 35]

(polymerization inhibitor)

G-1: 1,4-benzoquinone

G-2: 4-Methoxyphenol

(migration inhibitor)

H-1: 1,2,4-triazole

H-2: 1H-tetrazole

<evaluation>

<<Evaluation of mechanical properties>>

On the silicon wafer with the copper metal layer formed on the surface, the resin composition is spin-coated until the film thickness after curing becomes about 10 μm. After drying, a temperature-programmed curing furnace (VF-2000 model, KOYO THERMO SYSTEMS CO., LTD.), the atmosphere in the furnace was adjusted to the conditions described in the following table, and the cured film was obtained by heating under the conditions described in the following table. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were adjusted with nitrogen replacement and an oxygen concentration meter (manufactured by Yokogawa Electric Corporation).

The obtained cured film was cut into short strips with a width of 3 mm using a cutting machine (DAD3350 model, manufactured by DISCO Corporation), and then peeled from the silicon wafer using 46% hydrofluoric acid. The ductility of the cured film peeled from the silicon wafer was measured, and the mechanical properties were evaluated based on the following standards. Use a tensile testing machine (UTM-II-20 model, manufactured by ORIENTEC Co., LTD), The ductility of the cured film was measured according to ASTM D882-09.

A: Ductility is over 60%

B: Ductility is more than 50% and less than 60%

C: Ductility is more than 40% and less than 50%

D: Ductility is less than 40%

<Copper Corrosion>

The resin composition was spin-coated on the copper substrate until the cured film thickness became about 10 μm. After drying, a temperature-programmed curing furnace (VF-2000 model, manufactured by KOYO THERMO SYSTEMS CO., LTD.) was used to cure the inside of the furnace. The atmosphere was adjusted to the conditions described in the following table, and the cured film was obtained by heating under the conditions described in the following table. In addition, the oxygen partial pressure and oxygen concentration of the atmosphere in the furnace were adjusted with nitrogen replacement and an oxygen concentration meter (manufactured by Yokogawa Electric Corporation).

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

Regarding the copper substrate (bare substrate) before the cured film is formed and the copper substrate (copper substrate 1) after peeling off the cured film formed on the surface, surface observation (confirmation of discoloration/corrosion) using an optical microscope (manufactured by NIKON CORPORATION) and Cross-sectional observation (confirmation of film thickness fluctuations/concave-convexity) using a scanning electron microscope (manufactured by Hitachi, Ltd.) was used to evaluate the copper corrosion resistance based on the following criteria.

A: There is no discoloration/corrosion or film thickness change on the copper substrate 1. The unevenness is the same as that of the bare substrate.

B: Compared with the bare substrate, copper substrate 1 has a slightly darker purple color, but there is no change in film thickness or unevenness.

C: The purple color of the copper substrate 1 is slightly darker than that of the bare substrate, and the copper is slightly damaged and becomes slightly uneven.

D: The copper substrate 1 turns darker purple than the bare substrate, and the copper is damaged and has severe unevenness.

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

Claims (9)

A method for manufacturing a cured film, which includes: adding a polyimide precursor selected from polyimide precursors and polybenzoyl

The step of applying a resin composition of at least one polymer precursor in the group of azole precursors and a radically polymerizable monomer to a substrate to form a film; and heating the film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa Hardening steps. The manufacturing method of the cured film according to claim 1, wherein the atmospheric pressure of the heating and hardening step is 0.08~0.12MPa. The manufacturing method of the cured film according to claim 1 or 2, wherein in the step of heating and hardening, the film is heated to 170~350°C. The method for manufacturing a cured film according to claim 1 or 2, wherein between the step of forming the film and the step of heating and curing, a step of exposing the film and a step of developing the exposed film are included. The method for manufacturing a cured film according to claim 1 or 2, wherein the substrate to which the resin composition is applied is a metal substrate or a substrate including a metal layer. The method for manufacturing a cured film according to claim 1 or 2, which is a method for manufacturing a cured film used for an insulating layer. A cured film obtained by the method for manufacturing a cured film according to claim 1. A method for manufacturing a laminated body, which includes the steps of forming a cured film by the method of manufacturing a cured film according to any one of claims 1 to 6, and forming a metal layer on the surface of the cured film. A method of manufacturing a semiconductor element, which includes the method of manufacturing a cured film according to any one of claims 1 to 6.