JP2021128183A - Pattern formation method, photosensitive resin composition, method for manufacturing laminate, and method for manufacturing electronic device - Google Patents

Abstract

To provide a pattern formation method for suppressing pattern peeling of a pattern to be formed, a photosensitive resin composition used in the pattern formation method, a method for manufacturing a laminate including the pattern formation method, and a method for manufacturing an electronic device including the pattern formation method.SOLUTION: There are provided: a pattern formation method that includes an exposure step and a development step of selecting and exposing a photosensitive film formed of a photosensitive resin composition, in which the exposure step includes exposure with light having a first wavelength and exposure with light having a second wavelength, at least the one light is a laser beam, a difference between the first wavelength and the second wavelength is 5 nm or more, the exposure region with the first wavelength and the exposure region with the second wavelength at least partially overlap each other, and the composition contains a photosensitive compound and a specific resin; a photosensitive resin composition used in the pattern formation method; a method for manufacturing a laminate including the pattern formation method; and a method for manufacturing an electronic device including the pattern formation method.SELECTED DRAWING: None

Description

The present invention relates to a pattern forming method, a photosensitive resin composition, a method for producing a laminate, and a method for producing an electronic device.

Resins such as polyimide and polybenzoxazole are used in various applications because they have excellent heat resistance and insulating properties. The application is not particularly limited, and examples of electronic devices for mounting include the use of a pattern containing these resins as a material for an insulating film or a sealing material, or as a protective film. In addition, patterns containing these resins are also used as base films and coverlays for flexible substrates.

For example, in the above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of these resins or photosensitive resin compositions containing precursors of these resins.
A cured resin can be formed on the substrate by applying such a photosensitive resin composition to the substrate by, for example, coating, and then exposing, developing, heating, etc., if necessary. ..
Since the photosensitive resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the photosensitive resin composition to be applied. It can be said that it has excellent adaptability. In addition to the high performance of polyimide, polybenzoxazole, etc., from the viewpoint of excellent manufacturing adaptability, industrial application development of photosensitive resin compositions containing these resins is expected more and more.

For example, Patent Document 1 contains (A) a polyimide precursor and (B) a photosensitizer.
Described is a photosensitive resin composition in which the polyimide precursor (A) is a resin having a structural unit of an amic acid ester having a specific structure.

Japanese Unexamined Patent Publication No. 2018-165819

Conventionally, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, and a photosensitive resin composition containing a photosensitive compound have been applied to a substrate. Patterns have been formed by exposure and development.
Here, there is still room for improvement in suppressing the pattern peeling of the formed pattern.

The present invention relates to a pattern forming method in which pattern peeling of a formed pattern is suppressed, a photosensitive resin composition used in the pattern forming method, a method for producing a laminate including the pattern forming method, and the pattern forming method. It is an object of the present invention to provide a method for manufacturing an electronic device including.

Examples of typical embodiments of the present invention are shown below.
<1> An exposure step of selectively exposing a photosensitive film formed from a photosensitive resin composition, and
Including a developing step of developing the exposed photosensitive film to obtain a pattern.
The exposure process includes exposure with light having a first wavelength and exposure with light having a second wavelength.
At least one of the light having the first wavelength and the light having the second wavelength is laser light.
The difference between the first wavelength and the second wavelength is 5 nm or more.
Of the photosensitive film, at least a part of the first region exposed by the light having the first wavelength and the second region exposed by the light having the second wavelength overlap.
The photosensitive resin composition comprises a photosensitive compound and at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
Pattern formation method.
<2> The pattern according to <1>, wherein the photosensitive compound includes a first photosensitive compound that is exposed to the first wavelength and a second photosensitive compound that is exposed to the second wavelength. Forming method.
<3> The pattern forming method according to <1> or <2>, wherein the first wavelength is 200 to 400 nm.
<4> The pattern forming method according to any one of <1> to <3>, wherein the second wavelength is 300 to 500 nm.
<5> The pattern forming method according to any one of <1> to <4>, wherein both the light having the first wavelength and the light having the second wavelength are laser light.
<6> The pattern forming method according to any one of <1> to <5>, wherein the developer used in the development step is a developer containing an organic solvent.
<7> The pattern forming method according to any one of <1> to <6>, wherein the development in the development step is a negative type development.
<8> The pattern forming method according to any one of <1> to <7>, wherein the film thickness of the photosensitive film used in the exposure step is 5 to 50 μm.
<9> Described in any one of <1> to <8>, wherein the ratio of the area of the overlapping portion of the first region and the second region to the total area of the first region is 80% or more. Pattern formation method.
<10> The pattern forming method according to any one of <1> to <9>, wherein the resin is a polyimide precursor.
<11> The pattern forming method according to any one of <1> to <10>, wherein the photosensitive resin composition further contains a sensitizer.
<12> A photosensitive resin composition used for forming the photosensitive film in the pattern forming method according to any one of <1> to <11>.
<13> A method for producing a laminate, which comprises the pattern forming method according to any one of <1> to <11>.
<14> A method for manufacturing an electronic device, which comprises the pattern forming method according to any one of <1> to <11>, or the method for manufacturing a laminate according to <12>.

According to the present invention, a pattern forming method in which pattern peeling of a formed pattern is suppressed, a photosensitive resin composition used in the pattern forming method, a method for producing a laminate including the pattern forming method, and the pattern. A method of manufacturing an electronic device, including a forming method, is provided.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or , Either, and "(meth) acryloyl" means both "acryloyl" and "methacryloyl", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive film, the direction from the base material to the photosensitive film is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

(Pattern formation method)
The pattern forming method of the present invention includes an exposure step of selectively exposing a photosensitive film formed from a photosensitive resin composition and a developing step of developing the exposed photosensitive film to obtain a pattern. The process includes exposure to light having a first wavelength and exposure to light having a second wavelength, and at least one of the light having the first wavelength and the light having the second wavelength is laser light. The difference between the first wavelength and the second wavelength is 5 nm or more, and the photosensitive film has the first region exposed by the light having the first wavelength and the second wavelength. At least a part of the second region exposed by light overlaps, and the photosensitive resin composition comprises a group consisting of a photosensitive compound and a polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor. Contains at least one selected resin.
Hereinafter, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor is also referred to as "specific resin".

According to the pattern forming method of the present invention, pattern peeling of the above pattern is suppressed.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

In the conventional pattern forming method, for example, a film made of a photosensitive resin composition containing a precursor such as a polyimide precursor or a polybenzoxazole precursor is exposed to a single wavelength, and then developed to obtain a pattern. Has been done to form.
When the exposure is performed with a single wavelength in this way, for example, in the case of a negative type, the exposure light does not easily reach the deep part of the film, so that the pattern tends to be reverse-tapered, and the pattern In the case of the positive type, which is prone to peeling, it is necessary to expose the deep part of the film with a sufficient exposure amount in order to form a pattern, but when the exposure amount is increased, ablation occurs and the pattern collapses. It was found that pattern peeling may occur due to reasons such as the tendency for the pattern to peel off.
In addition, the use of laser light has been studied in order to allow the exposure light to reach the deep part of the film. However, the present inventors have considered, for example, when the exposure intensity is increased by using laser light of a single wavelength. It was found that there is a problem that the upper part of the pattern is easily destroyed by ablation or the like.
Therefore, as a result of diligent studies by the present inventors, the light having the first wavelength and the light having the first wavelength, which includes the exposure by the light having the first wavelength and the exposure by the light having the second wavelength in the exposure process, and the light having the first wavelength, and the light having the first wavelength, The present invention has been completed by finding that pattern peeling is suppressed by setting at least one of the light having the second wavelength to be laser light.
The mechanism by which the effect is obtained by the above aspect is unknown, but by performing exposure using a plurality of exposure lights having different wavelengths, at least one of which is a laser beam, the exposure light easily reaches a deep part, and the exposure with a resin is used. Since the absorption of light is also easily suppressed, it is presumed that the pattern peeling is suppressed.

Further, according to the pattern forming method described in the present invention, a pattern having excellent chemical resistance can be obtained because the solubility of the residual pattern is reduced due to the improvement of the resolution.
Specifically, for example, a polar solvent such as dimethylsulfoxide (DMSO) or N-methylpyrrolidone (NMP), an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, or the polar solvent and the alkaline aqueous solution. It is considered that a pattern in which the solubility and dispersibility in the mixed solution are suppressed can be obtained.
As described above, when the pattern is excellent in chemical resistance, for example, when another composition containing a solvent is further applied and cured on the pattern formed by the pattern forming method of the present invention to prepare a laminate, etc. In addition, even if the pattern is in contact with a developing solution or other composition, dissolution of the pattern is suppressed, even if the pattern is used under conditions in contact with a chemical such as a solvent or in an atmosphere in which a chemical such as a solvent is present. It is considered that there are advantages such as suppression of dissolution, dispersion or denaturation of the pattern.

Further, for example, Patent Document 1 describes that exposure including light of various wavelengths is performed using a high-pressure mercury lamp, but exposure by light having a first wavelength and light having a second wavelength are used. There is no description about an aspect in which at least one of the light having the first wavelength and the light having the second wavelength including the exposure is laser light.

Hereinafter, the pattern forming method of the present invention will be described in detail.

<Exposure process>
The pattern forming method of the present invention includes an exposure step of selectively exposing a photosensitive film formed from a photosensitive resin composition.
Selective exposure refers to exposing a part of the photosensitive film, and is also referred to as "pattern exposure".
In the exposure step, the photosensitive compound is exposed to light, and the solubility of the photosensitive film in a developing solution changes.
Specifically, for example, when the photosensitive compound is a photopolymerization initiator or a photoacid generator described later, and the specific resin contains a crosslinkable group, the photosensitive film contains a crosslinker, or both. Crosslinking progresses in the photosensitive film, and the solubility of the photosensitive film in the developing solution after the exposure step decreases.
For example, when the photosensitive compound is a photoacid generator described later and the developing solution is an alkaline developing solution described later, an acid is generated in the photosensitive film and the solubility in the developing solution is increased.
For example, when the photosensitive compound is a photoacid generator described later and the developing solution is an organic solvent described later, an acid is generated in the photosensitive film and the solubility in the developing solution is lowered.
For example, when the photosensitive compound is a photobase generator described later and the specific resin contains at least one of a polyimide precursor and a polybenzoxazole precursor described later, cyclization of the specific resin proceeds in the photosensitive film, and the cyclization proceeds with respect to the developing solution. Solubility decreases.
As described above, in the exposure step, for example, the photosensitivity of the photosensitive compound promotes the bonding reaction between the crosslinkable group contained in the specific resin or the crosslinking agent and another group, so that the developing solution of the photosensitive film is subjected to the reaction. The solubility may change, the solubility of the photosensitive film in the developer may change depending on the product generated by the chemical change due to the photosensitivity of the photosensitive compound, or the developer of the photosensitive film may change due to the cyclization of a specific resin. Solubility for may vary.

[Photosensitive film]
The photosensitive film used in the exposure step is a film formed from the photosensitive resin composition described later. Examples of the method for forming a photosensitive film from the photosensitive resin composition include the methods described in the film forming step described later.

The photosensitive film used in the pattern forming method of the present invention may be a negative type photosensitive film or a positive type photosensitive film.
The positive type photosensitive film means a photosensitive film in which the exposed part (exposed part) is removed by the developing solution in the exposure process, and the negative type photosensitive film means the part not exposed in the exposure process (non-exposed part). Refers to a photosensitive film that is removed by the developing solution.

In the present invention, the film thickness of the photosensitive film used in the exposure step is preferably 5 to 50 μm, more preferably 10 to 30 μm.

[Light with a first wavelength and light with a second wavelength]
The exposure step includes exposure with light having a first wavelength (hereinafter, also referred to as "first exposure") and exposure with light having a second wavelength (hereinafter, also referred to as "second exposure"). including.

-Exposure wavelength-
In the present invention, the first wavelength is a wavelength shorter than the second wavelength.
The difference between the first wavelength and the second wavelength is 5 nm or more, preferably 10 nm or more, and more preferably 20 nm or more.
The wavelength difference is defined as the difference between the wavelength of the highest intensity light in the first exposure and the wavelength of the highest intensity light in the second exposure.
When both the first exposure and the second exposure are performed by laser light, the above difference is defined as the difference in the maximum wavelength of each laser light.

The first wavelength and the second wavelength may be set as wavelengths to which the photosensitive compound or the sensitizer is exposed, respectively, but 200 to 550 nm is preferable, and 300 to 450 nm is more preferable.
The first wavelength and the second wavelength can be set as two wavelengths having the above-mentioned difference from the above-mentioned range, respectively.
The first wavelength is preferably 200 to 400 nm, more preferably 300 to 380 nm.
The second wavelength is preferably 300 to 550 nm, more preferably 350 to 450.
Further, the first wavelength is preferably 350 to 380 nm, the second wavelength is preferably 390 to 450 nm, the first wavelength is 360 to 380 nm, and the second wavelength is 390 to 420 nm. More preferred.

-Exposure timing-
The first exposure and the second exposure may be performed at the same time, may be performed so that a part of each exposure time overlaps, or may be performed so that the exposure times do not overlap. May be good.
Further, the first and second descriptions in the first exposure and the second exposure do not represent the order of the start order, end order, etc. of the exposure in the time series. For example, the first exposure may be started before the second exposure, or the second exposure may be started before the first exposure. Further, the first exposure may be completed before the second exposure, or the second exposure may be completed before the first exposure. As described above, the order of the first exposure and the second exposure in the time series is not particularly limited.
An example of the mode in which the first exposure and the second exposure are performed at the same time is a mode in which the first exposure and the second exposure are started at the same time and ended at the same time.
Examples of a mode in which the above parts overlap include a mode in which the second exposure is started after the first exposure is started and before the end of the first exposure, and a mode in which the second exposure is started and then the second exposure is started. An embodiment in which the first exposure is started before the end of the second exposure can be mentioned. Further, for example, the first exposure and the second exposure may be started at the same time, and one of the first exposure and the second exposure may be finished first.
Further, as an example of the embodiment in which the exposure times are not overlapped, an embodiment in which the first exposure is started and then the second exposure is started after the first exposure is completed, and the second exposure is started. After that, an embodiment in which the first exposure is started after the end of the second exposure and the like can be mentioned. In this embodiment, the time from the end of the first exposure to the start of the second exposure, or the time from the end of the second exposure to the start of the first exposure is not particularly limited, but is, for example, 0.1. It can be from seconds to 24 hours and the like.

-Laser light-
At least one of the light having the first wavelength and the light having the second wavelength is laser light.
From the viewpoint of suppressing pattern peeling, it is also preferable that both the light having the first wavelength and the light having the second wavelength are laser light.
Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Lasers and amplifiers that produce monochromatic light with stronger coherence and directivity by amplifying and oscillating light waves by utilizing the phenomenon of stimulated emission that occurs in substances with an inversion distribution, crystals, glass, liquids, dyes as excitation media, There is a gas or the like, and a laser having an oscillation wavelength in known ultraviolet light such as a solid-state laser, a liquid laser, a gas laser, or a semiconductor laser can be used from these media. Among them, a semiconductor laser, a solid-state laser, and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.
It is considered that the productivity of the pattern is likely to be excellent because the curing proceeds rapidly by using the laser beam for the exposure.
Since the laser light has good parallelism, it is possible to reduce the irradiation site (laser spot diameter, irradiation width, etc.). Therefore, it is possible to perform pattern exposure (direct exposure) without using a photomask when exposing by a method such as moving a photosensitive film or a laser light source using laser light. According to such an aspect, it is considered that the productivity is further improved because the steps of designing, manufacturing, installing, and removing the photomask can be omitted.
Further, when it is desired to suppress the influence of the shape or profile of the output light on the obtained pattern shape, it is also preferable to perform pattern exposure using a photomask even when the laser light is used as a light source. ..
Furthermore, by using laser light, there are advantages such as easy removal of unnecessary wavelengths, easy improvement of light illuminance (exposure intensity), shortening of exposure time, and extension of the life of the exposure light source. exist.

Specific examples of the laser light source include the second harmonic (532 nm) and third harmonic (355 nm) of the Nd: YAG laser, which is a solid-state laser with a particularly large output and relatively inexpensive, and the KrF (248 nm) of the excimer laser. , XeCl (308 nm), XeF (353 nm), semiconductor lasers (375 nm, 405 nm, 445 nm, 488 nm) and the like can be preferably used.

-Other light sources-
In the present invention, it is also preferable that one of the light having the first wavelength and the light having the second wavelength is light other than the laser light.
Examples of light sources other than laser light include metal halide lamps, high-pressure mercury lamps, extreme ultraviolet rays, electron beams, and the like.
In order to make the difference between the first wavelength and the second wavelength within the above range, an optical filter or the like that removes a specific wavelength from these light sources may be used.
When a light source other than laser light is used as the light source, it is preferable to perform pattern exposure using a photomask.

-Exposure area-
Of the photosensitive film, at least a part of the first region exposed by the light having the first wavelength and the second region exposed by the light having the second wavelength may overlap. The ratio of the area of the overlapping portion between the first region and the second region to the total area of the first region is preferably 80% or more, and more preferably 90% or more. The upper limit of the above ratio is not particularly limited, and may be 100% or less.
Further, the ratio of the area contained in the first region to the total area of the region included in at least one of the first region and the second region is preferably 50% or more, and is preferably 70% or more. Is more preferable. The upper limit of the above ratio is not particularly limited, and may be 100% or less.

-Exposure-
From the viewpoint of productivity and resolution, as each of the exposure in the first exposure and the second exposure is ^preferably in the range of ^{25mJ / cm 2 ~3,000mJ / cm 2} , 50mJ / cm 2 ~2, more preferably in the range of 000mJ / cm ^2, a range of 100mJ / cm ² ~1,000mJ / cm 2 is more preferable.
Moreover, the range from the viewpoint of productivity and resolution, the total exposure amount in the exposure ^step, preferably in the range of ^{50mJ / cm 2 ~3,000mJ / cm 2} , of 75mJ / cm ² ~2,000mJ / cm 2 still more ^preferably, a range of 100mJ / cm ² ~1,000mJ / cm 2 is more preferable.

-Other exposures-
The exposure step may further include exposures other than the first exposure and the second exposure.
Examples of other exposures include exposure with light having a wavelength different from that of the first wavelength and the second wavelength, exposure with broadband light, and the like.

<Post-exposure heating process>
The pattern forming method of the present invention may include a step of heating the photosensitive film after exposure (post-exposure heating step) after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50 ° C. to 140 ° C., more preferably 60 ° C. to 120 ° C.
The heating time in the post-exposure heating step is preferably 1 minute to 300 minutes, more preferably 5 minutes to 120 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature.
Further, the heating rate may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.

<Film formation process>
The pattern forming method of the present invention may include a film forming step of forming a photosensitive film from a photosensitive resin composition.
The photosensitive film in the exposure step may be a photosensitive film formed in the film forming step, or may be a photosensitive film obtained by means such as purchase.
The film forming step is preferably a step of applying the photosensitive resin composition to a substrate to form a film (layered) to obtain a photosensitive film.

〔Base material〕
The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film thin film) array substrate, plasma display panel (PDP) electrode plate, and the like. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular (disk-shaped) or rectangular (on the rectangular plate).
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

When a photosensitive film is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

Coating is preferable as a means for applying the photosensitive resin composition to the substrate.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive film, the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable, and from the viewpoint that the effect of the present invention can be easily obtained, the slit coating method is preferable. A photosensitive film having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material. For a circular base material such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead conditioner (EBR), air knife and the like.

<Drying process>
The pattern forming method of the present invention may include a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step).
The preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Development process>
The pattern forming method of the present invention includes a developing step of developing the photosensitive film after the exposure step with a developing solution to obtain a pattern.
By developing, one of the exposed portion and the non-exposed portion is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a process in which they are combined. It can be adopted.

Development is carried out using a developing solution. As the developing solution, one in which the unexposed part (non-exposed part) is removed in the case of negative type development, and one in which the exposed part (exposed part) is removed in the case of positive type development. , Can be used without any restrictions.
In the present invention, from the viewpoint of resolution and the like, the development in the development step is preferably negative type development.
In the present invention, the case where an alkaline developer is used as the developer is called alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is called solvent development.
Among these, the developer used in the present invention is preferably a developer containing an organic solvent, and more preferably a developer containing 50% by mass or more of an organic solvent.

In alkaline development, the developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developing solution, more preferably 5% by mass or less, and 1% by mass or less. Is more preferable, and a developer containing no organic solvent is particularly preferable.
The developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 15.
Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium acid, ammonia or amine. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide and the like can be mentioned. Of these, an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
When TMAH is used, for example, the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total amount of the developing solution. More preferred.
The alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.

In solvent development, the developer preferably contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. , Keto Examples of compounds include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene and the like. , Dimethyl sulfoxide is preferably mentioned as the sulfoxides.

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

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.

In the developing step, after the treatment with the developing solution, further rinsing may be performed.
In the case of solvent development, it is preferable to rinse with an organic solvent different from the developing solution.
In the case of alkaline development, rinsing is preferably performed using pure water.
The rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The pattern forming method of the present invention may further include a heating step of heating the pattern after the exposure step.

In the heating step, for example, a cyclization reaction of a polyimide precursor, a polybenzoxazole precursor, or the like proceeds.
In addition, cross-linking of unreacted cross-linking groups with a specific resin or a cross-linking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and even more preferably 160 to 350 ° C.
The heating rate from the temperature at the start of heating to the maximum heating temperature in the heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. Productivity can be ensured by setting the temperature rise rate to 1 ° C./min or more, and residual stress of the pattern can be relaxed by setting the temperature rise rate to 12 ° C./min or less.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes.
In particular, when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the pattern. The reason is not clear, but it is conceivable that the cross-linking reaction between the cross-linking groups in the specific resin or the cross-linking agent between the layers is proceeding within the above temperature range.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

<Exposure process after development>
The pattern forming method of the present invention may further include a post-development exposure step of exposing the pattern after the development step in place of or in addition to the heating step.
In the post-development exposure step, for example, a photobase generator or the like, which is a photosensitive compound described later, is exposed to light, and cyclization of a polyimide precursor, a polybenzoxazole precursor, or the like proceeds to obtain a cured pattern.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
Exposure in the developing after the exposure step, at an exposure energy conversion at a wavelength which the photosensitive compound is sensitive is preferably 100~20,000mJ / cm ^2, more be a 200~15,000mJ / cm ² preferable.
The post-development exposure step can be performed using, for example, light having the above-mentioned first wavelength, light having the above-mentioned second wavelength, light using these in combination, broadband light such as a high-pressure mercury lamp, and the like. It is preferable to use light.

<Metal layer forming process>
The pattern forming method of the present invention is a metal layer forming step of forming a metal layer on the surface of a pattern after a developing step (after being subjected to these steps when at least one of a heating step and a post-developing exposure step is included). Is preferably included.

As the metal layer, existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten and alloys containing these metals are exemplified, and copper and alloys containing these metals are exemplified. Aluminum is more preferred, copper is even more preferred.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<Use>
Examples of the fields to which the pattern obtained by the pattern forming method of the present invention can be applied include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.

The pattern obtained by the pattern forming method of the present invention is also used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, use for etching molded parts, and manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics. It can also be used.

(Manufacturing method of laminated body)
The method for producing a laminate of the present invention preferably includes the pattern forming method of the present invention.
The laminate obtained by the method for producing a laminate of the present invention is a laminate containing two or more layers of patterns, and may be a laminate in which 3 to 7 layers are laminated.
At least one of the two or more layers of the pattern contained in the laminate is a pattern obtained by the pattern forming method of the present invention, and from the viewpoint of suppressing the shrinkage of the pattern or the deformation of the pattern due to the shrinkage. It is also preferable that all the patterns contained in the laminated body are patterns obtained by the pattern forming method of the present invention.
It is preferable that the laminated body contains two or more patterns and includes a metal layer between any of the patterns. The metal layer is preferably formed by the metal layer forming step.
As the laminated body, for example, a laminated body including at least a layer structure in which three layers of a first pattern, a metal layer, and a second pattern are laminated in this order is preferable.
Both the first pattern and the second pattern are preferably patterns obtained by the pattern forming method of the present invention. The photosensitive resin composition of the present invention used for forming the first pattern and the photosensitive resin composition of the present invention used for forming the second pattern are compositions having the same composition. It may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Laminating process>
The method for producing a laminated body of the present invention preferably includes a laminating step.
The laminating step is again (a) film forming step (layer forming step), (b) exposure step, (c) developing step, (d) heating step and developing on the surface of the pattern (resin layer) or metal layer. This is a series of steps including performing at least one of the post-exposure steps in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. Needless to say, the laminating step may further include the drying step and the like as appropriate.

When the laminating step is further performed after the laminating step, after the exposure step, at least one of the heating step and the post-development exposure step, or after the metal layer forming step, a surface activation treatment step is further performed. May be done. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a configuration in which the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a configuration in which 3 or more and 5 or less are used is more preferable. ..
The composition, shape, film thickness, etc. of each of the above layers may be the same or different.

In the present invention, it is particularly preferable to form a pattern (resin layer) of the photosensitive resin composition so as to cover the metal layer after the metal layer is provided. Specifically, at least one of (a) film forming step, (b) exposure step, (c) developing step, (d) heating step and post-developing exposure step is repeated in the order of (e) metal layer forming step. Aspects are mentioned. By alternately performing the steps (a) to (d) for forming the pattern and the metal layer forming step, the pattern and the metal layer can be alternately laminated.

(Manufacturing method of electronic device)
The present invention also discloses a method for forming a pattern of the present invention or a method for manufacturing an electronic device including a method for manufacturing a laminate of the present invention. As specific examples of the electronic device in which the photosensitive resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
Hereinafter, the details of the photosensitive resin composition used in the pattern forming method of the present invention, the method for producing a laminate of the present invention, or the method for producing an electronic device of the present invention will be described.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention is a photosensitive resin composition used for forming the photosensitive film in the pattern forming method of the present invention, the method for producing a laminate of the present invention, or the method for producing an electronic device of the present invention. It is a thing.
That is, the photosensitive resin composition of the present invention contains a photosensitive compound and at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.

<Photosensitive compound>
The photosensitive compound preferably contains a first photosensitive compound that is photosensitive at the first wavelength and a second photosensitive compound that is photosensitive at the second wavelength.
By including the first photosensitive compound that the photosensitive compound is sensitive to at the first wavelength and the second photosensitive compound that is sensitive to the second wavelength, the photosensitive compound is photosensitive at the first wavelength and the second wavelength. A photosensitive film can be formed.
In the above aspect, the first photosensitive compound may or may not be exposed to the second wavelength. Further, the second photosensitive compound may or may not be sensitive to the first wavelength.
Further, as the photosensitive compound, in addition to the photosensitive compound (for example, the first photosensitive compound and the second photosensitive compound described above) that are exposed in the exposure step, the photosensitive compound that is exposed in the post-development exposure step is further added. It may be included.
The photosensitive compound that is exposed in the post-development exposure step is preferably a photosensitive compound that is not exposed in the exposure step but is exposed in the post-development exposure step.

Whether or not the photosensitive compound is sensitive to light of a certain wavelength is determined by the following method.
The photosensitive compound and polymethylmethacrylate (PMMA) are dissolved in methylethylketone to prepare a composition for forming a model film. The content of the photosensitive compound in the composition for forming a model film with respect to the total mass of the photosensitive compound and PMMA is 0.5 mmol / g. Further, the amount of methyl ethyl ketone used with respect to the total mass of the photosensitive compound and PMMA in the composition for forming a model film may be appropriately set according to the film thickness of the model film described later.
When the photosensitive resin composition contains a sensitizer described later, the content mass ratio of the photosensitive compound and the sensitizer in the photosensitive resin composition and the content mass ratio of the photosensitive compound and the sensitizer in the model film. A sensitizer is also added to the model film so that the content ratio is the same as that of.
The weight average molecular weight of PMMA is 10,000.
Then, the obtained composition for forming a model film is applied onto glass and heat-dried at 80 ° C. for 1 minute to obtain a model film. The film thickness of the model film should be 10 μm. Then, the composition film is exposed with the same wavelength and irradiation amount as the exposure in the first exposure or the second exposure using the same light source as the first exposure or the second exposure in the exposure step.
After the exposure, the model film and the glass on which the model film is formed are immersed in a methanol / THF = 50/50 (mass ratio) solution for 10 minutes while applying ultrasonic waves. The residual ratio of the photosensitive compound is calculated from the following formula by analyzing the extract extracted into the above solution by HPLC (high performance liquid chromatography).
Residual rate of photosensitive compound (%) = Content of photosensitive compound contained in model film after exposure (mol) / Content of photosensitive compound contained in model film before exposure (mol) × 100
Further, when the residual ratio of the photosensitive compound is less than 80%, it is determined that the photosensitive compound is a compound that is sensitive to the first wavelength or the second wavelength. The residual rate is preferably 70% or less, more preferably 60% or less, and further preferably 50% or less. The lower limit of the residual rate is not particularly limited and may be 0%.
When the residual ratio of the photosensitive compound is 80% or more, it is determined that the photosensitive compound is a compound that is not photosensitive at the first wavelength or the second wavelength. The residual rate is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. The upper limit of the residual rate is not particularly limited and may be 100%.

Further, it is preferable that the first photosensitive compound and the second photosensitive compound have different maximum absorption wavelengths. The difference in the maximum absorption wavelength between the first photosensitive compound and the second photosensitive compound is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 20 nm or more.
The maximum absorption wavelength of the photosensitive compound is defined as a wavelength existing on the longest wavelength side of the maximum absorption wavelengths in the wavelength range of 190 to 450 nm.

As a preferred embodiment of the pattern forming method of the present invention, as a photosensitive compound, a photoradical polymerization initiator having a maximum absorption wavelength in the vicinity of a wavelength of 365 nm and a photoradical polymerization initiator having a maximum absorption wavelength in the vicinity of a wavelength of 405 nm are included. Examples thereof include an embodiment in which the photosensitive resin composition is used and the first wavelength is 350 to 380 nm and the second wavelength is 390 to 420 nm.

It is also preferable that the photosensitive resin composition contains a photosensitive compound that is photosensitive at the first wavelength and the second wavelength.
Further, it is also one of the preferable embodiments that the photosensitive resin composition contains a photosensitive compound and a sensitizer. For example, the photosensitive resin composition contains a photosensitive compound that is sensitive to one of the first wavelength and the second wavelength, and a sensitizer that is sensitive to the other wavelength, so that the first wavelength and the second wavelength are present. A photosensitive film that is sensitive to two wavelengths can be formed.

A photosensitive compound is a compound that undergoes a chemical change such as generating a radical, an acid, or a base in an exposure process, and has an action of changing the solubility of a photosensitive film in a developing solution with the structural change. It is more preferable that the compound is a compound that generates radicals by the exposure step.
Further, the photosensitive compound is preferably a photopolymerization initiator, a photoacid generator or a photobase generator.
When the photosensitive compound contains a first photosensitive compound that is sensitive to the first wavelength and a second photosensitive compound that is sensitive to the second wavelength, the first photosensitive compound and the second photosensitive compound are sensitive. The compounds may be in a different category from the compounds, but are preferably compounds in the same category.
The above-mentioned compounds in different categories refer to an embodiment in which the first photosensitive compound is a photopolymerization initiator and the second photosensitive compound is a photoacid generator.
The above-mentioned compounds in the same category include, for example, an embodiment in which the first photosensitive compound is a photopolymerization initiator and the second photosensitive compound is also a photopolymerization initiator, and the first photosensitive compound is A mode in which the photoacid generator is a photoacid generator and the second photosensitive compound is also a photoacid generator, or the first photosensitive compound is a photobase generator and the second photosensitive compound is also a photobase generator. A mode that is an agent.
Among these, it is preferable that both the first photosensitive compound and the second photosensitive compound are photopolymerization initiators, and it is more preferable that both are photoradical polymerization initiators.

[Photopolymerization initiator]
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
The photoradical polymerization initiator is a compound that generates radicals in the exposure process.

-Photoradical polymerization initiator-
The photosensitive resin composition of the present invention preferably contains a photoradical polymerization initiator as the photosensitive compound.
For example, the photosensitive resin composition contains at least one of a photoradical polymerization initiator, a specific resin having a radically polymerizable ethylenically unsaturated bond, and a radical cross-linking agent described later, whereby radical polymerization is carried out. As a result, the solubility of the exposed portion of the photosensitive film in the developing solution decreases, so that a negative pattern can be formed.
The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known compounds, for example. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

The photoradical polymerization initiator is a compound having at least a molar extinction coefficient of ^{about 50 L · mol -1} · cm ^-1 with respect to light having a wavelength in the range of about 300 to 800 nm (preferably 330 to 500 nm). It is preferable that one type is contained. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description of paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and these contents are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

As hydroxyacetophenone-based initiators, IRGACURE 184 (IRGACURE is a registered trademark), Irgacure 1173, DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF), Omnirad 184, 2959, Omnirad 127 (trade name: both manufactured by IGM Resolution) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resins). ) Can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF), Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins) can be used.

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

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

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

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxy. Iminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime compound, which is a photoradical polymerization initiator, has a linking group represented by> C = N—O—C (= O) − in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or ^{biphenyl, R I01} is a group represented by formula ^(II), the same as ^{R I00} The groups, R ^{I02 to} R ^I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms or halogens, respectively.

In the formula, R ^{I05 to} R ^I07 are the same as ^{R I 02 to} R I ⁰⁴ of the above formula (I).

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

When the photosensitive resin composition contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator may be 0.1 to 30% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photoradical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photoradical polymerization initiators are contained, the total is preferably in the above range.

[Photoacid generator]
The photosensitive resin composition of the present invention preferably contains a photoacid generator as the photosensitive compound.
By containing the photoacid generator, for example, acid is generated in the exposed part of the photosensitive film, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part is removed by the developing solution. A positive relief pattern can be obtained.
Further, when the photosensitive resin composition contains a photoacid generator and a cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by the acid generated in the exposed portion, and the exposed portion is in the non-exposed portion. It is also possible to make it more difficult to remove by the developing solution. According to such an aspect, a negative type relief pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.

The quinone diazide compound includes a polyhydroxy compound in which quinone diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone diazide sulfonic acid is ester-bonded and a sulfonamide bond. Examples include those bound by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.

Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all of which are Fujifilm sum). Examples thereof include Kojunyaku Co., Ltd., Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF).

When the photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.

[Photobase generator]
The photosensitive resin composition of the present invention may contain a photobase generator as a photosensitive compound.
When the photosensitive resin composition contains a photobase generator and a cross-linking agent described later, for example, the cyclization of the specific resin is promoted by the base generated in the exposed portion, and the cross-linking reaction of the cross-linking agent is promoted. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A.M. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. et al. Shirai, and M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H. et al. Araki, M. et al. Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those in which the amidin moiety is latent by salt formation with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.
In the present invention, as the photobase generator, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like can be mentioned as more preferable examples.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization ratio, the basic substance preferably has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software is used as pKa.

From the viewpoint of storage stability of the photosensitive resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator. It is preferable that there is no charge on the top. As a photobase generator, it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Further, from the viewpoint of chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in the structure.

Further, for the above reasons, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in JP-A-2009-08452 and JP-A-2009 / 123122, JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, Carbamoyl. Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.

In addition, as the photobase generator, the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.

In addition, a commercially available product may be used as the photobase generator. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry Co., Ltd.) and the like.

When a photobase generator is contained, the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.

<Specific resin>
The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
The photosensitive resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator as a photosensitizer, contains a photoradical polymerization initiator as a photosensitizer, and contains a radical crosslinker. It is more preferable that the photosensitizer contains a photoradical polymerization initiator, a radical cross-linking agent, and a sensitizer. From such a photosensitive resin composition, for example, a negative photosensitive layer is formed.
Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator as the photosensitizer. From such a photosensitive resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.

式（２）中、Ａ^１及びＡ^２は、それぞれ独立に、酸素原子又はＮＨを表し、Ｒ^１１１は、２価の有機基を表し、Ｒ^１１５は、４価の有機基を表し、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子又は１価の有機基を表す。 [Polyimide precursor]
The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
Equation (2)

In formula (2), A ¹ and A ² 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 independently represent a hydrogen atom or a monovalent organic group.

^{A 1} and A ² in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
^{R 111} in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms. A cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by -Ar-L-Ar- is exemplified. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −CO−, −S−. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:

式中、Ａは、単結合、又は、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−ＳＯ_２−、ＮＨＣＯ−、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、又は、−ＳＯ_２−から選択される基であることがより好ましく、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、又は、−Ｃ（ＣＨ_３）_２−であることが更に好ましい。
式中、＊は他の構造との結合部位を表す。

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−, −SO. ₂ -, NHCO-, or is preferably a group selected from these combinations, a single bond, an alkylene group having carbon atoms which may be have 1-3 substituted with a fluorine atom, -O -, - C ( = O) -, - S-, or, -SO ₂ -, more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, - C (CF 3 ) ₂ − or −C (CH ₃ ) ₂ − is more preferable.
In the formula, * represents the binding site with other structures.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-a) Minophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3 , 3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4 '-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4, 4'-Diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, Diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluoro Butane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2 , 2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4 '-Bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro) Methylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2 -Bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino At least one diamine selected from -2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl. Can be mentioned.

Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/0385898 are also preferable.

Further, a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.

R ¹¹¹ is preferably represented by −Ar−L−Ar− from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −CO−, −S−. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO ₂ - are preferred. The aliphatic hydrocarbon group here is preferably an alkylene group.

式（５１）中、Ｒ^５０〜Ｒ^５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ^５０〜Ｒ^５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基である。
Ｒ^５０〜Ｒ^５７の１価の有機基としては、炭素数１〜１０（好ましくは炭素数１〜６）の無置換のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフッ化アルキル基等が挙げられる。

式（６１）中、Ｒ^５８及びＲ^５９は、それぞれ独立に、フッ素原子又はトリフルオロメチル基である。
式（５１）又は（６１）の構造を与えるジアミン化合物としては、２，２’−ジメチルベンジジン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，２’−ビス（フルオロ）−４，４’−ジアミノビフェニル、４，４’−ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種で又は２種以上を組み合わせて用いてもよい。 Further, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)

In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group or trifluoro. It is a methyl group.
The ^{monovalent organic groups of R 50 to} R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

式（５）中、Ｒ^１１２は、単結合、又は、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、及びＮＨＣＯ−、並びに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−ＣＯ−、−Ｓ−及びＳＯ_２−から選択される基であることがより好ましく、−ＣＨ_２−、−Ｃ（ＣＦ_３）_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−ＣＯ−、−Ｓ−及びＳＯ_２−からなる群から選択される２価の基であることが更に好ましい。 ^{R 115} in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * represents a binding site with another structure.
Equation (5)

In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, −O−, −CO−, −S−, −SO. _2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. -, - more preferably a group selected _from, -CH ₂ - - S- and _{SO 2, - C (CF 3} ) 2 -, - C (CH 3) 2 -, - O -, - CO -, - and more preferably a divalent radical selected from the group consisting of _- S-, and SO 2.

Equation (6)

式（Ｏ）中、Ｒ^１１５は、４価の有機基を表す。Ｒ^１１５の好ましい範囲は式（２）におけるＲ^１１５と同義であり、好ましい範囲も同様である。 Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Equation (O)

In formula (O), R ¹¹⁵ represents a tetravalent organic group. A preferred range of R ¹¹⁵ has the same meaning as ^{R 115} in formula (2), and preferred ranges are also the same.

Specific examples of tetracarboxylic acid dianhydrides include pyromellitic acid dianhydrides (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydrides, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3' , 4,4'-Diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5 , 7-Naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5, 6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4 5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis (2, 3-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and these Examples thereof include alkyl having 1 to 6 carbon atoms and an alkoxy derivative having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.

It is also preferable that at least one of R ¹¹¹ and R ^{115 has an OH group.} More specifically, ^{as R 111} , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and both contain a polymerizable group. preferable. The polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino. The group is mentioned. As the radically polymerizable group contained in the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- or a polyalkyleneoxy group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group are more preferable, and organic film. From the viewpoint of facilitating the filling of the formula (1) or the formula (2), the polyalkyleneoxy group is more preferable.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are independently hydrogen atoms or monovalent organic groups. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a boronyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acrydin ring, phenanthrolin ring, It is a thianthracene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferred.

In the formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, even if the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. good. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

At ^{least one of R 113} and R ¹¹⁴ may be a polarity converting group such as an acid degradable group. The acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

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 preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

式（２−Ａ）中、Ａ^１及びＡ^２は、酸素原子を表し、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、２価の有機基を表し、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^１１３及びＲ^１１４の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。 The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (2-A)

In formula (2-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. Representing a hydrogen atom or a monovalent organic group ^{, at least one of R 113} and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.

^{A 1, A 2, R 111} , R 113 and ^{R 114} each independently have the same meaning as ^{A 1, A 2, R 111} , R 113 and ^{R 114} in formula (2), and preferred ranges are also the same ..
R ¹¹² has the same meaning as ^{R 112} in formula (5), and preferred ranges are also the same.

The polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more of all repeating units, further 70 mol% or more, particularly 90 mol% or more is a repeating unit represented by the formula (2) is used. Illustrated.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
Further, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
In the present specification, the "main chain" refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other binding chains.

− Fluorine atom −
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a fluorine atom.
The fluorine atom is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described later, or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group ^{in R 132} in the repeating unit represented by 4) ^{or R 131} in the repeating unit represented by the formula (4) described later.
The amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.

-Silicon atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.
The silicon atom is ^{preferably contained in R 131} in the repeating unit represented by the formula (4) described later, and is organically modified (poly ^{) in R 131} in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure.
Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

-Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferably provided at the side chain.
The ethylenically unsaturated bond preferably has radical polymerization property.
The ethylenically unsaturated bond is ^{preferably contained in R 132} in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later. ^{It is more preferable that R 132} in the repeating unit represented by (4) ^{or R 131} in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
Of these, ethylenically unsaturated bond, ethylene R ¹³¹ in the repeating unit represented by the preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted, which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group, and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferable.

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH (OH) CH _2- , -C (= O) O-, -O (C = O) NH-. , A (poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1 ~ 6 is more preferable, and 1-3 are particularly preferable), or a group in which two or more of these are combined is represented.

式（Ｒ１）〜（Ｒ３）中、Ｌは単結合、又は、炭素数２〜１２のアルキレン基、炭素数２〜３０の（ポリ）アルキレンオキシ基若しくはこれらを２以上結合した基を表し、Ｘは酸素原子又は硫黄原子を表し、＊は他の構造との結合部位を表し、●は式（ＩＩＩ）中のＲ^２０１が結合する酸素原子との結合部位を表す。
式（Ｒ１）〜（Ｒ３）中、Ｌにおける炭素数２〜１２のアルキレン基、又は、炭素数２〜３０の（ポリ）アルキレンオキシ基の好ましい態様は、上述のＲ^２１における、炭素数２〜１２のアルキレン基、又は、炭素数２〜３０の（ポリ）アルキレンオキシ基の好ましい態様と同様である。
式（Ｒ１）中、Ｘは酸素原子であることが好ましい。
式（Ｒ１）〜（Ｒ３）中、＊は式（ＩＶ）中の＊と同義であり、好ましい態様も同様である。
式（Ｒ１）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物（例えば、２−イソシアナトエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ２）で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物（例えば、２−ヒドロキシエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ３）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物（例えば、グリシジルメタクリレート等）とを反応することにより得られる。 Among these, R ²¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded, and X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which ^{R 201 in the formula (III) is bonded.}
In the formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R ²¹ having 2 to 12 carbon atoms. This is the same as the preferred embodiment of 12 alkylene groups or (poly) alkyleneoxy groups having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * is synonymous with * in formula (IV), and the preferred embodiment is also the same.
The structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.

In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.

The amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

-Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained ^{in R 131} in the repeating unit represented by the formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

− Polarity converter −
The polyimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value-
When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving the developability. Is more preferable.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is preferably contained ^{in, for example, R 132} in the repeating unit represented by the formula (4) described later, or R ^{131 in the repeating unit represented by the formula (4) described later.}
The amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

式（４）中、Ｒ^１３１は、２価の有機基を表し、Ｒ^１３２は、４価の有機基を表す。
重合性基を有する場合、重合性基は、Ｒ^１３１及びＲ^１３２の少なくとも一方に位置していてもよいし、下記式（４−１）又は式（４−２）に示すようにポリイミドの末端に位置していてもよい。
式（４−１）

式（４−１）中、Ｒ^１３３は重合性基であり、他の基は式（４）と同義である。
式（４−２）

Ｒ^１３４及びＲ^１３５の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式（４）と同義である。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). More preferably, it is a compound containing a repeating unit and having a polymerizable group.
Equation (4)

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When having a polymerizable group, the polymerizable group ^{may be located at at least one of R 131} and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
Equation (4-1)

In formula (4-1), ^R133 is a polymerizable group, and the other groups are synonymous with formula (4).
Equation (4-2)

At ^{least one of R 134} and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. ^{Examples of the divalent organic group include those similar to R 111} in the formula (2), and the preferred range is also the same.
Further, as R ¹³¹ , a diamine residue remaining after removal of the amino group of diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic and aromatic diamines. ^{Specific examples include the example of R 111} in the formula (2) of the polyimide precursor.

It is preferable that R ¹³¹ is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably, a diamine residue containing no aromatic ring.

Examples of diamines containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples include, but are not limited to, propoxy) propoxy-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine, and the like.

R ¹³² represents a tetravalent organic group. ^{Examples of the tetravalent organic group include those similar to R 115} in the formula (2), and the preferred range is also the same.
For example, ^{four conjugates of a tetravalent organic group exemplified as R 115} combine with four −C (= O) − moieties in the above formula (4) to form a fused ring.

In addition, R ¹³² includes a tetracarboxylic acid residue remaining after removal of an anhydride group from the tetracarboxylic dianhydride. Specific examples include an example of R ^{115 in} the polyimide precursor formula (2). From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ^{132 has an OH group.} More specifically, ^{as R 131} , 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, and (DA-1) to (DA-18) above are preferred examples. As R ¹³² , the above (DAA-1) to (DAA-5) are more preferable examples.

It is also preferable that the polyimide has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

Further, in order to improve the storage stability of the composition, the main chain end of polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. preferable. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

− Imidization rate (ring closure rate) −
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured by, for example, the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near ^{1377 cm -1, which is the absorption peak derived from the imide structure.} Next, the polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of ^{1377 cm -1.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

The polyimide may contain the repeating structural unit of the above formula (4), all containing one type of R ¹³¹ or R ^132, and the above formula (4) containing two or more different types of R ¹³¹ or R ^132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).

Imide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal encapsulant which is a monoactive ester compound) to obtain a diester by tetracarboxylic acid dianhydride and alcohol, and then diamine (partly monoamine). A method of reacting in the presence of a condensing agent with (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.

式（３）中、Ｒ^１２１は、２価の有機基を表し、Ｒ^１２２は、４価の有機基を表し、Ｒ^１２３及びＲ^１２４は、それぞれ独立に、水素原子又は１価の有機基を表す。 [Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
Equation (3)

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group. show.

In the formula (3), R ¹²³ and R ^{124 are synonymous with R 113} in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid composed of is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelliic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, nonadecandioic acid, eikosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosandioic acid, heptacosanedioic acid, octacosanedioic acid, nonakosandioic acid, tria Examples thereof include contandioic acid, hentoriacontandioic acid, dotoriacontandioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.

（式中、Ｚは炭素数１〜６の炭化水素基であり、ｎは１〜６の整数である。）

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.

式中、Ａは−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、及び、−Ｃ（ＣＨ_３）_２−からなる群から選択される２価の基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。

In the formula, A is -CH _2- , _{-O-, -S-, -SO 2-} , -CO-, -NHCO-, -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- Represents a divalent group selected from the group consisting of, and each independently represents a binding site with another structure.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (2), and the preferable range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-) 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-dihydroxy-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bis-aminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferable.

式中、Ｘ_１は、−Ｏ−、−Ｓ−、−Ｃ（ＣＦ_３）_２−、−ＣＨ_２−、−ＳＯ_２−、−ＮＨＣＯ−を表し、＊及び＃はそれぞれ、他の構造との結合部位を表す。Ｒは水素原子又は１価の置換基を表し、水素原子又は炭化水素基が好ましく、水素原子又はアルキル基がより好ましい。また、Ｒ^１２２は、上記式により表される構造であることも好ましい。Ｒ^１２２が、上記式により表される構造である場合、計４つの＊及び＃のうち、いずれか２つが式（３）中のＲ^１２２が結合する窒素原子との結合部位であり、かつ、別の２つが式（３）中のＲ^１２２が結合する酸素原子との結合部位であることが好ましく、２つの＊が式（３）中のＲ^１２２が結合する酸素原子との結合部位であり、かつ、２つの＃が式（３）中のＲ^１２２が結合する窒素原子との結合部位であるか、又は、２つの＊が式（３）中のＲ^１２２が結合する窒素原子との結合部位であり、かつ、２つの＃が式（３）中のＲ^１２２が結合する酸素原子との結合部位であることがより好ましく、２つの＊が式（３）中のＲ^１２２が結合する酸素原子との結合部位であり、かつ、２つの＃が式（３）中のＲ^１２２が結合する窒素原子との結合部位であることが更に好ましい。

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, ^{it is also preferable that R 122} has a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the four * and # in total are the binding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bonded, and} preferably R ¹²² in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R ¹²² are attached in the formula (3) ^{, And two # are the binding sites with the nitrogen atom to which R 122} in the formula (3) is bound, or two * are the binding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bound.} It is more preferable that the site is a site ^{and the two #s} are the binding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the oxygen to which ^{the R 122 in the formula (3) is bonded.} It is more preferable that the binding site is a binding site with an atom and the ^{two #s} are the binding sites with a nitrogen atom to which R 122 in the formula (3) is bonded.

In the formula (As), R ₁ is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO _2- , -CO-, -NHCO-, a single bond, or the following formula (A-s). It is an organic group selected from the group of sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

（式（Ａ−ｓｃ）中、＊は上記式（Ａ−ｓ）で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。）

(In the formula (A-sc), * indicates that it binds to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

The formula (A-s) in the ortho position of the phenolic hydroxyl groups, i.e., to have also substituent R ₃ is believed to closer the distance of the carbonyl carbon and the hydroxyl group of the amide bond was cured at a low temperature It is particularly preferable in that the effect of increasing the cyclization rate is further enhanced.

Further, in the above formula (As), _{it is said that the fact that R 2} is an alkyl group and R ₃ is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.

Further, in the above formula (As), _{it is more preferable that R 1} is an alkylene or a substituted alkylene. Specific examples of the alkylene and the substituted alkylene according to R ₁ include linear or branched alkylene groups having 1 to 8 carbon atoms, among which −CH ₂ − and _{−CH (CH 3).} )-, -C (CH ₃ ) ₂ -has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that a well-balanced polybenzoxazole precursor can be obtained.

As a method for producing the bis-aminophenol derivative represented by the above formula (As), for example, paragraph numbers 0085-0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A are referred to. These contents can be incorporated herein by reference.

Specific examples of the structure of the bis-aminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506A, and these contents are described in the present specification. Incorporated in. Of course, it goes without saying that it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.

式（ＳＬ）中、Ｚは、ａ構造とｂ構造を有し、Ｒ^１ｓは、水素原子又は炭素数１〜１０の炭化水素基であり、Ｒ^２ｓは炭素数１〜１０の炭化水素基であり、Ｒ^３ｓ、Ｒ^４ｓ、Ｒ^５ｓ、Ｒ^６ｓのうち少なくとも１つは芳香族基で、残りは水素原子又は炭素数１〜３０の有機基で、それぞれ同一でも異なっていてもよい。ａ構造及びｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分のモル％は、ａ構造は５〜９５モル％、ｂ構造は９５〜５モル％であり、ａ＋ｂは１００モル％である。

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms. ^Yes , at least one of R 3s, R ^4s , R ^5s , and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.

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

When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.

式（Ｘ）中、Ｒ^１３３は、２価の有機基を表し、Ｒ^１３４は、４価の有機基を表す。
重合性基又は酸分解性基等の極性変換基を有する場合、重合性基又は酸分解性基等の極性変換基は、Ｒ^１３３及びＲ^１３４の少なくとも一方に位置していてもよいし、下記式（Ｘ−１）又は式（Ｘ−２）に示すようにポリベンゾオキサゾールの末端に位置していてもよい。
式（Ｘ−１）

式（Ｘ−１）中、Ｒ^１３５及びＲ^１３６の少なくとも一方は、重合性基又は酸分解性基等の極性変換基であり、重合性基又は酸分解性基等の極性変換基でない場合は有機基であり、他の基は式（Ｘ）と同義である。
式（Ｘ−２）

式（Ｘ−２）中、Ｒ^１３７は重合性基又は酸分解性基等の極性変換基であり、他は置換基であり、他の基は式（Ｘ）と同義である。 [Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable. Further, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-degradable group.

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
When having a polar converting group such as a polymerizable group or an acid-degradable group, the polar converting group such as a polymerizable group or an acid-degradable group ^{may be located at at least one of R 133} and R ¹³⁴ , and may be located at least one of the following. It may be located at the end of the polybenzoxazole as shown in the formula (X-1) or the formula (X-2).
Equation (X-1)

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group. It is an organic group, and the other groups are synonymous with the formula (X).
Equation (X-2)

In the formula (X-2), R ¹³⁷ is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).

A polar converting group such as a polymerizable group or an acid-degradable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic or aromatic group. ^{Specific examples include the example of R 121} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 121.}

R ¹³⁴ represents a tetravalent organic group. Examples of the ^{tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 122.}
For example, ^{four conjugates of a tetravalent organic group exemplified as R 122} combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, it forms the following structure. * Each independently represents a binding site with another structure.

The oxazoleization rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. When the oxazoleization rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

The polybenzoxazole may comprise a repeating structural unit of formula (X), all comprising one R ¹³¹ or R ^{132, and may include two or more different types of R 131} or R ^132. It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).

The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R ^133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This is obtained by oxazole using a known oxazole reaction method.
In the case of a dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.

[Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent such as thionyl chloride and then reacting it with a diamine.

It is also preferable to synthesize using a non-halogen catalyst without using the above halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples thereof include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.

In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.

-End sealant-
In order to further improve the storage stability in the method for producing a polyimide precursor or the like, the end of the polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

-Solid precipitation-
A step of precipitating a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran is dissolved in a soluble solvent to cause solid precipitation.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.

〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 50% by mass or more. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

<Other resins>
In addition to the above-mentioned specific resin, the composition of the present invention may further contain another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of an organic film, and the like.

When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

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

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-). Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropion Methyl acetate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate and the like.

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

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Crosslinking agent>
The photosensitive resin composition of the present invention preferably contains a cross-linking agent.
The cross-linking agent is preferably a cross-linking agent having a group whose bonding reaction with other groups is promoted by the exposure of the photosensitive compound in the above-mentioned exposure step.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.

<Radical cross-linking agent>
The photosensitive resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.

The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Further, from the viewpoint of the film strength of the obtained pattern, the photosensitive resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable. The compound having is more preferable.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern, the photosensitive resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable.

The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.

Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, which are preferably unsuitable. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993. Urethane (meth) acrylates, such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as a preferable radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups and cardo resins can also be used.

Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also used. It can be used as a radical cross-linking agent.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as radical cross-linking agents, and their contents are incorporated in the present specification.

As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd., Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylic (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable. These oligomer types can also be used.

Commercially available products of the radical cross-linking agent include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209 manufactured by Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-10. , UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based skeleton 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 are also suitable. Further, as the radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.

The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radical cross-linking agent provided with is more preferable. Particularly preferably, in a radical cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good. The acid value is measured according to the description of JIS K 0070: 1992.

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

When the radical cross-linking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Other cross-linking agents>
The photosensitive resin composition of the present invention preferably contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is covalently bonded to another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitive compound. It is preferable that the compound has a plurality of groups in the molecule for which the reaction for forming the above is promoted, and the reaction for forming a covalent bond with another compound in the composition or a reaction product thereof is an acid or a base. A compound having a plurality of groups promoted by the action in the molecule is preferable.
The acid or base is an acid or base generated from a photoacid generator or a photobase generator which is a photosensitive compound in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom. A compound having a structure directly bonded to is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.

Specific examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine and the like.

Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycoluryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). A compound to which a group is directly bonded is also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like can be mentioned.

Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikarak (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.

Further, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the photosensitive resin composition.

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol Propane Triglycidyl Ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples of the contained silicone and the like can be mentioned, but the present invention is not limited to these. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Servinus B0134, B0177 ( Product name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L , XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN -S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

[Oxetane compound (compound having an oxetanyl group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.

[Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA-type benzoxazine, B-m-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzo. Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.

The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other cross-linking agent may contain only one type, or may contain two or more types. When two or more other cross-linking agents are contained, the total is preferably in the above range.

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids or bases.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminosinnamiri Denindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocumine, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocumine, 3-methoxycarbonyl-7-diethylaminocumine, 3-ethoxycarbonyl-7-diethylamino Kumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naft (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide and the like.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

<Thermal polymerization initiator>
The photosensitive resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator may be contained. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, for example, when the pattern forming method of the present invention includes a heating step, the polymerization reaction of the resin and the polymerizable compound can be allowed to proceed, so that the chemical resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. More preferably, it is 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

<Thermal acid generator>
The photosensitive resin composition of the present invention may contain a thermoacid generator.
The thermoacid generator, for example, when the pattern forming method of the present invention includes a heating step, generates an acid by heating and has a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzo. It has the effect of promoting the cross-linking reaction of at least one compound selected from the oxazine compounds.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acids such as sulfonic acids are preferred. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935A.

Among them, those that generate alkyl sulfonic acid having 1 to 4 carbon atoms or haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonic acid (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-(((propylsulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o-tolyl) Propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as thermal acid generators.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part by mass or more, the cross-linking reaction is promoted, so that the mechanical properties and chemical resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

<Onium salt>
The composition of the present invention preferably contains an onium salt.
In particular, when the polyimide precursor is contained as the specific resin, the composition preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

Further, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermobase generator.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.
Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

When the composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Thermal base generator>
The composition of the present invention may contain a thermobase generator.
In particular, when the composition contains a polyimide precursor as a specific resin, the composition preferably contains a thermobase generator.
The thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of other thermobase generators include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, ^{none of Rb 1} , Rb ² and Rb ³ has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

In formulas (B1) and (B2), ^{it is preferable that at least one of Rb 1} , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. A cyclohexyl group which may be used is more preferable.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6). 10 to 10 are more preferred), alkoxy groups (2 to 24 carbon atoms are preferred, 2 to 12 are more preferred, 2 to 6 are even more preferred), arylalkyl groups (7 to 23 carbon atoms are preferred, 7 to 19 are more preferred). Preferably, 7 to 12 are more preferable), an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2). 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 7 carbon atoms). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable). Among them, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent as long as the effect of the present invention is exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.
Rb ¹³ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2-8 are more preferable, 2-3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2-3 are more preferable), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

The molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.

The content of the thermobase generator is preferably 0.1 to 50% by mass with respect to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermobase generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Migration inhibitor>
The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive film.

The migration inhibitor is not particularly limited, but a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenol compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion trap agent that traps anions such as halogen ions can also be used.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, and is 0. .05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.

The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds can be used (Me is a methyl group).

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.

The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>
The photosensitive resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

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 JP-A-2014-191002, paragraphs of International Publication No. 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/0975994. Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..

The content of the metal adhesive improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<Other additives>
The photosensitive resin composition of the present invention contains various additives such as a surfactant, a chain transfer agent, a higher fatty acid derivative, an inorganic particle, and a curing agent, if necessary, as long as the effects of the present invention can be obtained. A curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an antioxidant and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

また、界面活性剤は、国際公開第２０１５／１９９２１９号の段落０１５９〜０１６５に記載の化合物を用いることもできる。 [Surfactant]
Each type of surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.

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

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

[Chain transfer agent]
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.

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

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

[Higher fatty acid derivative]
In the photosensitive resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the photosensitive resin composition is dried in the process of application and drying. It may be unevenly distributed on the surface of an object.

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

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative shall be 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<Restrictions on other contained substances>
The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

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

Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention. Methods such as filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

Considering the use as a semiconductor material, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

A conventionally known storage container can be used as the storage container for the photosensitive resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing impurities from being mixed into the raw materials and the photosensitive resin composition, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Use of photosensitive resin composition>
The photosensitive resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of an electronic device, forming a stress buffer film, and the like.

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

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the photosensitive resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, 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, "part" and "%" are based on mass.

<Synthesis Example 1: Synthesis of Polymer A-1>
9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride, oxydiphthalic dianhydride while removing moisture in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 10.0 g (32.25 mmol) of the product was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent solution over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain polymer A-1.

<Synthesis Example 2: Synthesis of Polymer A-2>
65.56 g (179 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. ) And 2.48 g (10 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 300 g of N-methylpyrrolidone (NMP). Subsequently, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40 ° C. for 2 hours. Then, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40 ° C. for 2 hours. After stirring, the temperature was raised to 180 ° C. while flowing nitrogen at a flow rate of 200 ml / min, and the mixture was stirred for 6 hours.
After cooling the above reaction solution to 25 ° C., 0.005 g of p-methoxyphenol was added and dissolved. To this solution, 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise, and the mixture was stirred at 25 ° C. for 2 hours and then at 60 ° C. for 3 hours. This was cooled to 25 ° C., 10 g of acetic acid was added, and the mixture was stirred at 25 ° C. for 1 hour. After stirring, the mixture was precipitated in 2 liters of water / methanol = 75/25 (volume ratio) and stirred at a rate of 2,000 rpm for 30 minutes. The precipitated polyimide resin was obtained by filtration, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain polymer A-2.

<Synthesis Example 3: Synthesis of Polymer A-3>
27.55 g (0.160 mol) of 1,4-cyclohexanedicarboxylic acid (cis-, trans-mixture, manufactured by Tokyo Chemical Industry Co., Ltd.) in a three-necked flask equipped with a thermometer, agitator, and a nitrogen introduction tube. 64.28 g of N-methyl-2-pyrrolidone (NMP) was added, and 38.07 g (0.320 mol) of thionyl chloride was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and an excess amount of thionyl chloride was distilled off under reduced pressure to obtain a 1,4-cyclohexanedicarboxylic acid dichloride (cis-, trans-mixture) as a 30 mass% NMP solution. rice field.
73.25 g (0.200 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP) in a three-necked flask equipped with a thermometer, stirrer and nitrogen inlet tube. -AF, manufactured by Central Glass Co., Ltd., 31.64 g (0.400 mol) of pyridine and 293 g of NMP were added. This was stirred at room temperature and then cooled to −15 ° C. in a dry ice / methanol bath. To this solution, while maintaining the reaction temperature at -5 ° C to -15 ° C, 30.11 g (0.144 mol) of a 30 mass% NMP solution of 1,4-cyclohexanedicarboxylic acid dichloride and 3.83 g (0.83 g (0.)). A mixed solution of 016 mol) of sebacoil chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 96.25 g of NMP was added dropwise. After the dropping was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, this reaction solution was cooled to -5 ° C or lower in an ice / methanol bath, and while maintaining the reaction temperature at −0 ° C or lower, 9.59 g (0.090 mol) of butyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) ) And 34.5 g of a mixed solution of NMP were added dropwise. After the dropping was completed, the mixture was further stirred for 16 hours.
The reaction was diluted with 550 g of NMP and placed in a vigorously stirred 4 L deionized / methanol (80/20 volume ratio) mixture, the precipitated white powder recovered by filtration and washed with deionized water. .. The polymer was dried at 50 ° C. for 2 days under vacuum to give resin A-1a.
25.00 g of resin A-1a, 125 g of NMP and 125 g of methyl ethyl ketone were added to the eggplant flask, and the mixture was concentrated under reduced pressure at 60 ° C. until the contents became 160 g. Here, 0.43 g (1.85 mmol) of camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.12 g (0.065 mol) of 2,3-dihydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) ) Was added, and the mixture was stirred at room temperature for 1.5 hours. To the obtained solution, 0.37 g of triethylamine and 150 g of NMP were added and diluted.
The resulting solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, the precipitated white powder was collected by filtration and washed with deionized water. The polymer was dried at 50 ° C. for 2 days under vacuum to give polymer A-3.

<Synthesis Example 4: Synthesis of Polymer A-4>
In Synthesis Example 1, except that 1.82 g (58.7 mmol) of 1,6-diaminohexane was used instead of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether, The reaction was carried out in the same manner as described to obtain polymer A-4.

<Synthesis Example 5: Synthesis of Polymer A-5>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (4,4'-oxydiphthalic acid dried at 140 ° C. for 12 hours) and 18.6 g (129 mmol) of 2- Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain 4,4'-oxydiphthalic acid. A diester with 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes, keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated by adding to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polymer A-5.

<Synthesis Example 6: Synthesis of Polymer A-6>
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , Dryed with a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while SOCL _{2 was added.} After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added to the reaction mixture over 20 minutes while keeping the temperature at -5 to 0 ° C. Dropped. Then, the solution and the reaction mixture were reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain polymer A-6.

<Examples and Comparative Examples>
In each example, the components shown in Table 1 or Table 2 below were mixed to obtain each photosensitive resin composition. Further, in the comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition.
Specifically, the content of the component shown in Table 1 or Table 2 is the amount shown in "Mass part" of Table 1 or Table 2. Further, in each composition, the solvent content was adjusted so that the solid content concentration (mass%) of the composition was the value shown in Table 1 or Table 2.
The obtained photosensitive resin composition and comparative composition were pressure-filtered at a pressure of 0.3 MPa through a filter made of polytetrafluoroethylene having a filter pore diameter of 0.8 μm.
Further, in Table 1 or Table 2, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Table 1 or Table 2 are as follows.

〔resin〕
-A-1 to A-6: Polymers A-1 to A-6 synthesized in the above synthesis example.

[Radical cross-linking agent]
-B-1: Tetraethylene glycol dimethacrylate-B-2: Dipentaerythritol hexaacrylate-B-3: Light ester BP-6EM (manufactured by Kyoei Kagaku Co., Ltd.)

[Acid cross-linking agent]
・ B-4: Nikarac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

[Photosensitive compound]
-C-1: Irgacure 784 (manufactured by BASF)
C-2: Irgacure OXE-01 (manufactured by BASF)
-C-3: ADEKA NCI-930 (manufactured by ADEKA Corporation)
C-4: Photoacid generator represented by the following formula (C-4) (BASF, PAG-103)

〔Silane coupling agent〕
-D-1: N- (3- (triethoxysilyl) propyl) phthalamide acid-D-2: Benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4' -Dicarboxylic acid-D-3: IM-1000 (manufactured by JX Nippon Mining & Metals Co., Ltd.)
-D-4: 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd., KBM-403)
D-5: N- [3- (triethoxysilyl) propyl] maleic acid monoamide

[Polymerization inhibitor]
-E-1: 2-nitroso-1-naphthol-E-2: 4-methoxyphenol (MEHQ)
-E-3: 4-Methoxy-1-naphthol-E-4: p-benzoquinone

〔Additive〕
F-1: A compound represented by the following formula (F-1) ・ F-2: 7- (diethylamino) coumarin-3-carboxylate ethyl ・ F-3: 1H-tetrazole ・ F-4: N-phenyl Diethanolamine F-5: 1,3-dibutylthiourea F-6: Megafuck F-554 (manufactured by DIC Co., Ltd.)

[Thermal acid generator]
G-1: Isopropyl p-toluenesulfonate

[Thermal base generator]
H-1: The compound represented by the following formula (H-1).

〔solvent〕
-S-1: N-methyl-2-pyrrolidone-S-2: Ethyl lactate-S-3: γ-butyrolactone-S-4: Dimethyl sulfoxide In Table 1 or Table 2, the description in the column of "ratio in solvent". Indicates the content (mass%) of each solvent with respect to the total mass of the solvent.

<Evaluation>
[Evaluation of pattern formation]
-Formation of photosensitive film-
The photosensitive resin composition or the comparative composition prepared in each Example and Comparative Example was spin-coated on a disk-shaped silicon wafer having a diameter of 200 mm (“A” was described in the “Applicable method” column, respectively). Example) or slit coating (example described as "B" in the "application method" column) was applied.
The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° C. for 5 minutes to form a photosensitive film on the silicon wafer.
As for the spin coating, the rotation speed was adjusted so that the film thickness after drying would be the film thickness shown in the “Film thickness (μm)” column of Table 1 or Table 2, and the spin coating was applied by rotating for 30 seconds. Regarding the slit coat, the distance between the substrate and the slit die is 200 μm, the distance between the liquid discharge ports of the slit die is 150 μm, and the film thickness after drying is described in the “Film thickness (μm)” column of Table 1 or Table 2. The amount of the discharged liquid was adjusted so as to have the same film thickness as the above.

-Exposure-
In the example described as "365" or the like in the column of "first exposure wavelength (nm)" in Table 1 or Table 2, the laser light having the described wavelength is defined as the light having the first wavelength. Exposure was performed with light having one wavelength. ,
In the example described as "365 (H)" or the like in the column of "first exposure wavelength (nm)" in Table 1 or Table 2, wavelengths other than the wavelengths described in ± 10 μm are selected by a bandpass filter. The cut high-pressure mercury lamp was used as light having a first wavelength, and exposure was performed with light having a first wavelength.
In the example described as "405" or the like in the column of "second exposure wavelength (nm)" in Table 1 or Table 2, the laser light having the described wavelength is defined as the light having the second wavelength. Exposure was performed with light having two wavelengths. ,
In the example in which "405 (H)" or the like is described in the column of "second exposure wavelength (nm)" in Table 1 or Table 2, wavelengths other than the wavelengths described in ± 10 μm are selected by a bandpass filter. The cut high-pressure mercury lamp was used as light having a second wavelength, and exposure was performed with light having a second wavelength.
In the example described as "M" in the "Exposure method" column of Table 1 or Table 2, exposure was performed using a binary mask having a width of 20 μm and a 1: 1 line-and-space pattern formed as a photomask. .. The irradiation amount (exposure amount) was set so that the energy per unit area was the same for all light sources.
In the example described as "D" in the "exposure method" column of Table 1 or Table 2, pattern exposure was performed directly without using a photomask. The exposure pattern was a 1: 1 line-and-space pattern with a width of 20 μm. The irradiation amount (exposure amount) was set so that the energy per unit area was the same for all light sources.
In the example described as "A" in the "Timing" column of Table 1 or Table 2, exposure with light having the first exposure wavelength and exposure with light having the second exposure wavelength were performed at the same time.
In the example described as "B" in the "Timing" column of Table 1 or Table 2, exposure with light having a second exposure wavelength was performed after the start of exposure with light having a first exposure wavelength. The start time of exposure with light having the second sound exposure wavelength was set to the time when half of the exposure time at the first exposure wavelength was completed.
In the example described as "C" in the "Timing" column of Table 1 or Table 2, the exposure with the light having the second exposure wavelength was started immediately after the end of the exposure with the light having the first exposure wavelength.
In the example described as "D" in the "Timing" column of Table 1 or Table 2, the exposure with the light having the second exposure wavelength is started 10 seconds after the end of the exposure with the light having the first exposure wavelength. bottom.
In Comparative Example 1, since only the exposure with the light having the first exposure wavelength was performed, “−” was described in the “Timing” column.
In the example described as "A" in the "overlapping area" column of Table 1 or Table 2, the region exposed by the light having the first exposure wavelength (first region) and the light having the second exposure wavelength. The exposure was performed with the region (second region) exposed by the above as the same region, and the ratio of the area of the overlapping portion of the first region and the second region to the total area of the first region was set to 100%.
In the example described as "B" in the "overlapping area" column of Table 1 or Table 2, the region (first region) exposed by light having the first exposure wavelength is used as a photomask and has a width of 20 μm. A region exposed by light having a first exposure wavelength using a binary mask in which a one-line and space pattern is formed, and a region exposed by light having a second exposure wavelength (second region) is a photo. Using a binary mask having a width of 16 μm and a 16:24 line-and-space pattern formed as a mask, exposure is performed as a region in which 2 μm is not exposed from both ends of the first region, and the first region with respect to the entire area of the first region is exposed. The ratio of the area of the overlapping portion of the second region was set to 80%.

-Development-
In the example in which "S" is described in the "Developer" column of Table 1 or Table 2, the exposed photosensitive film (resin layer) is developed with cyclopentanone at 25 ° C. for 60 seconds to form a line having a width of 20 μm. Formed an and-space pattern. Then, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min to reach the temperature described in the “Cure temperature (° C.)” column of Table 1 or Table 2, and then in Table 1 or Table 2. The temperature was maintained for the time described in the "Cure time (min)" column to form a pattern.
In the example described as "A" in the "Developer" column of Table 1 or Table 2, the exposed photosensitive film (resin layer) was subjected to a 2.3 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds. It was developed and washed with pure water to form a line-and-space pattern with a width of 20 μm. Then, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min to reach the temperature described in the “Cure temperature (° C.)” column of Table 1 or Table 2, and then in Table 1 or Table 2. The temperature was maintained for the time described in the "Cure time (min)" column to form a pattern.
The formed pattern was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and the presence or absence of pattern peeling was evaluated. Further, the pattern cross section was observed using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and the presence or absence of undercut was evaluated.
The obtained pattern-forming results were evaluated according to the following evaluation criteria, and the evaluation results are listed in the "Pattern-forming" column of Table 1 or Table 2. It is preferable that no pattern peeling is observed, and it is more preferable that neither pattern peeling nor undercut is observed.
-Evaluation criteria-
A: Neither pattern peeling nor undercut was observed.
B: No pattern peeling was observed, but undercut was observed.
C: Both pattern peeling and undercut were observed.

[Evaluation of chemical resistance]
-Calculation of dissolution rate-
In each Example or Comparative Example, the photosensitive film was formed on the silicon wafer by the same method as the formation of the photosensitive film in the above-mentioned evaluation of pattern formability.
Then, in each Example or Comparative Example in which a resin composition containing at least one of C-1 to C-3 or a comparative composition was used as the photosensitive compound, the "exposure method" of Table 1 or Table 2 was used. For the example described as "M" in the column, the entire surface of the photosensitive film was exposed without using a photomask, and for the example described as "D" in the "Exposure method" column of Table 1 or Table 2. Except that the entire surface of the photosensitive film was exposed to laser, exposure was performed by the same method as the exposure method in the evaluation of pattern formability described above to obtain a resin film.
In the examples using the resin composition containing C-4 as the photosensitive compound, no exposure was performed and the photosensitive film was used as a resin film.
Next, the resin film obtained in each Example or Comparative Example was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, and in the "Cure temperature (° C.)" column of Table 1 or Table 2. After reaching the stated temperature, the temperature was maintained for the time described in the "Cure time (min)" column of Table 1 or Table 2 to form a cured film.
The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated.
Chemicals: Mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the cured membrane in the chemicals at 75 ° C. for 15 minutes. The thickness of the cured film before and after was compared, and the dissolution rate (nm / min) was calculated.
The obtained dissolution rate values were evaluated according to the following evaluation criteria, and the evaluation results were listed in the "Chemical resistance" column of Table 1 or Table 2. It can be said that the lower the dissolution rate, the better the chemical resistance.
-Evaluation criteria-
A: The dissolution rate is less than 250 nm / min.
B: The dissolution rate is 250 nm / min or more and less than 500 nm / min.
C: The dissolution rate is 500 nm / min or more.

From the above results, it can be seen that the pattern forming method of the present invention suppresses pattern peeling as compared with the pattern forming method according to Comparative Example 1 in which exposure by light having a second wavelength is not performed.

<Example 101>
The photosensitive resin composition used in Example 1 was applied in layers to the surface of the thin copper layer of the resin substrate having the thin copper layer formed on the surface by a spin coating method, and dried at 100 ° C. for 2 minutes. After forming a photosensitive film having a film thickness of 20 μm, exposure was performed at an exposure amount of ^{400 mJ / cm 2} using a laser beam having a wavelength of 365 nm and a laser beam having a wavelength of 405 nm. Exposure was performed through a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 20 μm). After exposure, it was developed with cyclopentanone at 25 ° C. for 60 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
The pattern was cured by heating at 230 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating properties.
Further, when an electronic device was manufactured using the interlayer insulating film for the rewiring layer, it was confirmed that the electronic device operated without any problem.

Claims (14)

An exposure process that selectively exposes a photosensitive film formed from a photosensitive resin composition, and
A developing step of developing the exposed photosensitive film to obtain a pattern is included.
The exposure process includes exposure with light having a first wavelength and exposure with light having a second wavelength.
At least one of the light having the first wavelength and the light having the second wavelength is laser light.
The difference between the first wavelength and the second wavelength is 5 nm or more.
Of the photosensitive film, at least a part of the first region exposed by the light having the first wavelength and the second region exposed by the light having the second wavelength overlap.
The photosensitive resin composition comprises a photosensitive compound and at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
Pattern formation method. The pattern forming method according to claim 1, wherein the photosensitive compound comprises a first photosensitive compound that is exposed to the first wavelength and a second photosensitive compound that is exposed to the second wavelength. The pattern forming method according to claim 1 or 2, wherein the first wavelength is 200 to 400 nm. The pattern forming method according to any one of claims 1 to 3, wherein the second wavelength is 300 to 500 nm. The pattern forming method according to any one of claims 1 to 4, wherein both the light having the first wavelength and the light having the second wavelength are laser light. The pattern forming method according to any one of claims 1 to 5, wherein the developing solution used in the developing step is a developing solution containing an organic solvent. The pattern forming method according to any one of claims 1 to 6, wherein the development in the development step is a negative type development. The pattern forming method according to any one of claims 1 to 7, wherein the film thickness of the photosensitive film used in the exposure step is 5 to 50 μm. The pattern forming method according to any one of claims 1 to 8, wherein the ratio of the area of the overlapping portion of the first region and the second region to the total area of the first region is 80% or more. The pattern forming method according to any one of claims 1 to 9, wherein the resin is a polyimide precursor. The pattern forming method according to any one of claims 1 to 10, wherein the photosensitive resin composition further contains a sensitizer. A photosensitive resin composition used for forming the photosensitive film in the pattern forming method according to any one of claims 1 to 11. A method for producing a laminate, which comprises the pattern forming method according to any one of claims 1 to 11. A method for manufacturing an electronic device, which comprises the method for forming a pattern according to any one of claims 1 to 11 or the method for manufacturing a laminate according to claim 12.