JP7196121B2 - Pattern forming method, photosensitive resin composition, laminate manufacturing method, and electronic device manufacturing method - Google Patents

Description

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

Resins such as polyimide and polybenzoxazole are used in various applications because of their excellent heat resistance and insulating properties. The above applications are not particularly limited, but in the case of electronic devices for mounting, patterns containing these resins can be used as materials for insulating films and sealing materials, or as protective films. Patterns containing these resins are also used as base films and coverlays for flexible substrates.

For example, in the applications described above, resins such as polyimide and polybenzoxazole are used in the form of photosensitive resin compositions containing these resins or precursors of these resins.
Such a photosensitive resin composition is applied to a substrate, for example, by coating or the like, and then, by performing exposure, development, heating, etc. as necessary, a cured resin can be formed on the substrate. .
Since the photosensitive resin composition can be applied by a known coating method, for example, the shape, size, application position, etc. of the photosensitive resin composition to be applied have a high degree of freedom in design. It can be said that it is excellent in adaptability. In addition to the high performance possessed by polyimide, polybenzoxazole, etc., from the viewpoint of such excellent manufacturing applicability, the development of industrial applications of photosensitive resin compositions containing these resins is increasingly expected.

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

JP 2018-165819 A

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 are applied to the substrate, Patterns have been formed by exposure and development.
Here, there is still room for improvement in suppressing pattern peeling of the formed pattern.

The present invention provides 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 laminate manufacturing method including the pattern forming method, and the pattern forming method. An object of the present invention is to provide a method of manufacturing an electronic device including

Examples of representative embodiments of the present invention are provided 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;
wherein the exposing step comprises exposing with light having a first wavelength and exposing 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,
At least a portion of the first region of the photosensitive film exposed to light having the first wavelength and the second region exposed to light having the second wavelength overlap,
The photosensitive resin composition contains a photosensitive compound and at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors.
Pattern formation method.
<2> The pattern according to <1>, wherein the photosensitive compound comprises a first photosensitive compound that is sensitive at the first wavelength, and a second photosensitive compound that is sensitive at 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 developing 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 developing step is negative development.
<8> The pattern forming method according to any one of <1> to <7>, wherein the photosensitive film used in the exposure step has a thickness of 5 to 50 μm.
<9> 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, including the pattern forming method according to any one of <1> to <11>.
<14> An electronic device manufacturing method including the pattern forming method according to any one of <1> to <11> or the laminate manufacturing method 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 laminate manufacturing method including the pattern forming method, and the pattern Methods of manufacturing electronic devices are provided, including methods of forming.

Principal embodiments of the present invention are described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.
As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
As used herein, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Moreover, in this 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, weight average molecular weight (Mw) and 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, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below", it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be 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. In addition, unless otherwise specified, the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a photosensitive film, the direction from the base material to the photosensitive film is referred to as "upper". The opposite direction is called "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertically upward direction.
In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH, unless otherwise stated.
Combinations of preferred aspects are more preferred aspects herein.

(Pattern formation method)
The pattern forming method of the present invention comprises 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, and The step includes exposure with light having a first wavelength and exposure with light having a second wavelength, wherein at least one of the light having the first wavelength and the light having the second wavelength is laser light wherein the difference between the first wavelength and the second wavelength is 5 nm or more, and the photosensitive film has a first region exposed to light having the first wavelength and the second wavelength At least a portion of the second region exposed to light overlaps, and the photosensitive resin composition is selected from the group consisting of a photosensitive compound, a polyimide, a polyimide precursor, a polybenzoxazole, and a polybenzoxazole precursor. It contains at least one selected resin.
Hereinafter, at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors is also referred to as "specific resin".

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

In conventional pattern formation methods, 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 light with a single wavelength, and then developed to form a pattern. has been formed.
The present inventors have found that when exposure is performed with a single wavelength in this way, for example, in the case of a negative type, it is difficult for the exposure light to reach deep into the film, so the pattern tends to be inversely tapered, and the pattern If it is a positive type, it is necessary to perform exposure with a sufficient amount of exposure to the deep part of the film in order to form a pattern, but if the exposure amount is increased, ablation will occur and the pattern will collapse. It has been found that pattern peeling may occur due to reasons such as that the pattern is likely to occur.
In addition, the use of laser light has also been studied in order to allow the exposure light to reach deep into the film. It has been found that there is a problem that the upper part of the pattern is likely to be destroyed by abrasion or the like.
Therefore, as a result of intensive studies by the present inventors, the exposure step includes exposure with light having a first wavelength and exposure with light having a second wavelength, and light having the first wavelength, and The present inventors have found that pattern peeling can be suppressed by using laser light as at least one of the light having the second wavelength and completed the present invention.
Although the mechanism by which the effect is obtained by the above aspect is unknown, by performing exposure using a plurality of exposure lights with different wavelengths, at least one of which is a laser beam, the exposure light can easily reach deep, and the resin can be exposed. It is presumed that pattern peeling is suppressed because light absorption is easily suppressed.

In addition, according to the pattern forming method of the present invention, a pattern having excellent chemical resistance can be obtained because the solubility of the residual pattern decreases due to the improvement in resolution.
Specifically, for example, polar solvents such as dimethylsulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, or the mixture of the polar solvent and the alkaline aqueous solution It is thought that a pattern with suppressed solubility and dispersibility in the mixed liquid can be obtained.
Thus, when the pattern is excellent in chemical resistance, for example, when another composition containing a solvent is further applied on the pattern formed by the pattern forming method of the present invention and cured to produce a laminate. In addition, even if the pattern is in contact with a developer or other composition, dissolution of the pattern is suppressed, even if the pattern is used under conditions where the pattern is in contact with chemicals such as solvents or in an atmosphere where chemicals such as solvents are present. It is believed that there are advantages such as inhibition of pattern dissolution, dispersion or denaturation.

Further, for example, Patent Document 1 describes that exposure including light of various wavelengths is performed using a high-pressure mercury lamp. It does not describe an embodiment in which at least one of the light having the first wavelength and the light having the second wavelength is laser light.

The pattern forming method of the present invention will be described in detail below.

<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.
The term "selectively exposing" refers to exposing a part of the photosensitive film, and is also called "pattern exposure".
In the exposure process, the photosensitive compound is exposed, and the solubility of the photosensitive film in the developer 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, or the photosensitive film contains a crosslinker, or both, Cross-linking progresses in the photosensitive film, and the solubility of the photosensitive film in the developer after the exposure process is lowered.
For example, when the photosensitive compound is a photo-acid generator described later and the developer is an alkali developer described later, acid is generated in the photosensitive film and the solubility in the developer increases.
For example, when the photosensitive compound is a photoacid generator described later and the developer is an organic solvent described later, acid is generated in the photosensitive film and the solubility in the developer is reduced.
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 developer reacts with the developer. Solubility decreases.
As described above, in the exposure step, for example, the exposure of the photosensitive compound promotes the bonding reaction between the crosslinkable group contained in the specific resin or the crosslinker and other groups. The solubility may change, the solubility of the photosensitive film in the developer may change due to the product generated by the chemical change due to exposure of the photosensitive compound, or the developer of the photosensitive film may change due to the cyclization of the specific resin. may vary in solubility.

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

The photosensitive film used in the pattern forming method of the present invention may be a negative photosensitive film or a positive photosensitive film.
A positive photosensitive film is a photosensitive film from which the exposed portion (exposed portion) in the exposure process is removed by a developer, and a negative photosensitive film is a portion that is not exposed in the exposure process (non-exposed portion). refers to a photosensitive film that is removed by a developer.

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

[Light having a first wavelength and light having 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 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, more preferably 20 nm or more.
The wavelength difference is defined as the difference between the wavelength of the most intense light in the first exposure and the wavelength of the most intense light in the second exposure.
When both the first exposure and the second exposure are performed with laser light, the difference is defined as the difference in 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 sensitive, and are preferably 200 to 550 nm, more preferably 300 to 450 nm.
The first wavelength and the second wavelength can each be set as two wavelengths with the above difference from within the above range.
The first wavelength is preferably 200-400 nm, more preferably 300-380 nm.
The second wavelength is preferably 300-550 nm, more preferably 350-450 nm.
Further, it is preferable that the first wavelength is 350 to 380 nm and the second wavelength is 390 to 450 nm, and 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 simultaneously, may be performed so that the respective exposure times partially overlap, or may be performed so that the exposure times do not overlap. good too.
In addition, the first and second descriptions in the first exposure and the second exposure do not represent the order of exposure start order, end order, etc. in time series. For example, the first exposure may start before the second exposure, or the second exposure may start before the first exposure. Also, the first exposure may be completed before the second exposure, or the second exposure may be completed before the first exposure. Thus, the order of the first exposure and the second exposure in time series is not particularly limited.
An example of the mode of performing the simultaneous operations includes a mode in which the first exposure and the second exposure are started at the same time and finished at the same time.
Examples of aspects in which the above part overlaps include, for example, after starting the first exposure, starting the second exposure before the end of the first exposure, after starting the second exposure, Examples include a mode in which the first exposure is started before the end of the second exposure. Alternatively, 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 a mode in which the exposure times are performed so as not to overlap, a mode in which the second exposure is started after the first exposure is completed after the first exposure is started, and a mode in which the second exposure is started After that, the first exposure is started after the end of the second exposure. In this aspect, 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 for example 0.1 It can be from seconds to 24 hours, and so on.

－Laser beam－
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 be laser light.
Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators 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 population inversion. There are gases and the like, and known lasers having oscillation wavelengths in ultraviolet light, such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers, can be used from these media. Among them, semiconductor lasers, solid-state lasers, and gas lasers are preferable from the viewpoint of laser output and oscillation wavelength.
It is believed that the use of a laser beam for exposure facilitates excellent pattern productivity for reasons such as rapid progress of curing.
Since the laser beam has good parallelism, it is possible to reduce the irradiation area (laser spot diameter, irradiation width, etc.). Therefore, it is possible to perform pattern exposure (direct exposure) without using a photomask by using a laser beam and moving a photosensitive film or a laser light source. According to such a mode, it is possible to omit steps such as designing, manufacturing, installing, and removing the photomask, and thus it is considered that the productivity is further improved.
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 a preferred embodiment to carry out pattern exposure using a photomask even when a laser beam is used as the light source. .
Furthermore, by using laser light, it is easy to remove unnecessary wavelengths, or it is easy to improve the light illuminance (exposure intensity), shortening the exposure time, and prolonging the life of the exposure light source. exist.

As the laser light source, specifically, the second harmonic (532 nm) and third harmonic (355 nm) of the Nd:YAG laser, which is a relatively inexpensive solid-state laser with a particularly large output, and the KrF (248 nm) 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 be light other than laser light.
Light sources other than laser light include metal halide lamps, high-pressure mercury lamps, extreme ultraviolet rays, and electron beams.
In order to keep 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 may be used in these light sources.
When a light source other than laser light is used as the light source, pattern exposure using a photomask is preferably performed.

-Exposure area-
The first region of the photosensitive film exposed to the light having the first wavelength and the second region exposed to the light having the second wavelength may at least partially overlap, 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 preferably 80% or more, 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 included 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 70% or more. is more preferred. The upper limit of the above ratio is not particularly limited, and may be 100% or less.

-Exposure amount-
From the viewpoint of productivity and resolution, the respective exposure amounts in the first exposure and the second exposure are preferably in the range of 25 mJ/cm ² to 3,000 mJ/cm ² , 50 mJ/cm ² to 2, A range of 000 mJ/cm ² is more preferred, and a range of 100 mJ/cm ² to 1,000 mJ/cm ² is even more preferred.
From the viewpoint of productivity and resolution, the total exposure dose in the exposure step is preferably in the range of 50 mJ/cm ² to 3,000 mJ/cm ² , more preferably in the range of 75 mJ/cm ² to 2,000 mJ/cm ² . is more preferable, and a range of 100 mJ/cm ² to 1,000 mJ/cm ² is even more preferable.

-other exposure-
The exposure step may further include exposure other than the first exposure and the second exposure.
Other exposures include exposure with light having a wavelength different from 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 exposed photosensitive film (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, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
Also, the rate of temperature increase may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used.
Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.

<Film forming process>
The pattern forming method of the present invention may include a film forming step of forming a photosensitive film from the 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 of purchase or the like.
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 according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
In addition, these substrates may be provided with a layer such as an adhesion layer or an oxide layer on the surface.
As the base material, for example, a plate-like base material (substrate) is used.
Further, the shape of the substrate is not particularly limited, and may be circular (disk-like) or rectangular (rectangular plate-like).
As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. In the case of a rectangular shape, the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

Moreover, when forming a photosensitive film on the surface of a resin layer or the surface of a 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, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. Spin coating, slit coating, spray coating, and inkjet are more preferable from the viewpoint of uniformity of the thickness of the photosensitive film, and slit coating is preferable from the viewpoint of easily obtaining the effects of the present invention. A photosensitive film having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
Also, a step of removing excess film at the edge of the substrate may be performed. Examples of such processes include edge bead rinse (EBR), air knife, and the like.

<Drying process>
The pattern forming method of the present invention may include a step of drying the formed film (layer) to remove the solvent (drying step) after the film forming step (layer forming step).
The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 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.
One of the exposed portion and the non-exposed portion is removed by developing. The developing method is not particularly limited as long as a desired pattern can be formed. The development 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 or the like, and a combination thereof. Adoptable.

Development is performed using a developer. For negative development, the developer removes the unexposed areas (non-exposed areas), and for positive development, the exposed areas (exposed areas) are removed. can be used without any restrictions.
In the present invention, development in the development step is preferably negative development from the viewpoint of resolution and the like.
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 the organic solvent.

In alkaline development, the developer is preferably a developer having an organic solvent content of 10% by mass or less, more preferably 5% by mass or less, more preferably 1% by mass or less, with respect to the total mass of the developer. is more preferred, and a developer containing no organic solvent is particularly preferred.
The developer for alkaline development is more preferably an aqueous solution having a pH of 10-15.
Alkali compounds contained in the developer in alkali development include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, metasilicate. Potassium acid, ammonia, amines, and the like. 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. Among them, alkali compounds containing no metal are preferred, and ammonium compounds are more preferred.
The content of the basic compound in the developer, for example, when TMAH is used, is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass of the total amount of the developer. More preferred.
Alkaline compounds may be used alone or in combination of two or more. When two or more alkali compounds are used, the total is preferably within the above range.

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

Organic solvents include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. . ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., 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 (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as 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., and , keto and aromatic hydrocarbons such as toluene, xylene, anisole, and limonene. , and sulfoxides are preferably dimethyl sulfoxide.

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

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

In the development step, rinsing may be further performed after the treatment using the developer.
In the case of solvent development, rinsing is preferably performed with an organic solvent different from the developer.
In the case of alkali development, rinsing is preferably performed using pure water.
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, etc. proceeds.
In addition, cross-linking of unreacted cross-linkable groups in the specific resin or a cross-linking agent other than the specific resin also progresses.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 140 to 400°C, even more preferably 160 to 350°C.
In the heating step, the heating rate from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the temperature increase rate to 1° C./min or more, productivity can be ensured, and by setting the temperature increase rate to 12° C./min or less, the residual stress of the pattern can be relaxed.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, particularly preferably 30 to 240 minutes.
In particular, when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between pattern layers. The reason for this is not clear, but it is thought that the crosslinkable groups in the specific resin or crosslinker between the layers are undergoing a crosslink reaction by setting the temperature within the above range.

Heating may be done in stages. As an example, the temperature is raised from 25° C. to 180° C. at 3° C./min, held at 180° C. for 60 minutes, heated from 180° C. to 200° C. at 2° C./min, and held at 200° C. for 120 minutes. , may be performed. The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to carry out treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment step is preferably performed for 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, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

The heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
A 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.

<Post-development exposure process>
The pattern forming method of the present invention may further include a post-development exposure step of exposing the pattern after the development step instead 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, and cyclization of the polyimide precursor, polybenzoxazole precursor, or the like proceeds to obtain a cured pattern.
In the post-development exposure step, at least part of the pattern obtained in the development step may be exposed, but it is preferable to expose the entire pattern.
The exposure amount in the post-development exposure step is preferably 100 to 20,000 mJ/cm ² , more preferably 200 to 15,000 mJ/cm ² in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
The post-development exposure step can be performed using, for example, light having the first wavelength described above, light having the second wavelength described above, light using both of these, broadband light such as a high-pressure mercury lamp, and the like. It is preferred to use light.

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

The metal layer is not particularly limited, and existing metal species can be used, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals. Aluminum is more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods 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, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.

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

<Application>
Fields to which the pattern obtained by the pattern forming method of the present invention can be applied include insulating films of electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above may be used. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011 Published by the Japan Polyimide and Aromatic Polymer Research Group/Edited, "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc. can be referred to.

The patterns obtained by the patterning method of the present invention are also useful in the manufacture of plates such as offset or screen plates, for use in etching molded parts, in the manufacture of protective lacquers and dielectric layers in electronics, especially microelectronics. can also be used.

(Laminate manufacturing method)
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 obtained by laminating 3 to 7 layers.
At least one of the patterns of two or more layers included in the laminate is a pattern obtained by the pattern forming method of the present invention, and from the viewpoint of suppressing pattern shrinkage or pattern deformation accompanying the shrinkage. It is also preferable that all the patterns contained in the laminate are patterns obtained by the pattern forming method of the present invention.
It is preferable that the laminate includes two or more layers of patterns and a metal layer between any of the patterns. The metal layer is preferably formed by the metal layer forming step.
As the laminate, for example, a laminate 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 preferred.
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 have the same composition. or compositions having different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.

<Lamination process>
It is preferable that the method for manufacturing the laminate of the present invention includes a lamination step.
The lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, only the film forming step (a) may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, a (e) metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.

After the lamination step, when the lamination step is further performed, after the exposure step, after 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 performed. A plasma treatment is exemplified as the surface activation treatment.

The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a configuration in which the resin layers are 3 to 7 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferable, and a configuration in which 3 to 5 layers is more preferable. .
Each of the above layers may have the same composition, shape, film thickness, etc., or may differ from each other.

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 providing the metal layer. Specifically, (a) a film forming step, (b) an exposure step, (c) a developing step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step are repeated in this order. aspects. By alternately performing the steps (a) to (d) of forming the pattern and the step of forming the metal layer, the pattern and the metal layer can be alternately laminated.

(Method for manufacturing electronic device)
The present invention also discloses an electronic device manufacturing method including the pattern forming method of the present invention or the laminate manufacturing method of the present invention. Specific examples of electronic devices using the photosensitive resin composition of the present invention for forming an interlayer insulating film for a rewiring layer refer to paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. , the contents of which are incorporated herein.
Details of the photosensitive resin composition used in the pattern forming method of the present invention, the laminate manufacturing method of the present invention, or the electronic device manufacturing method of the present invention will be described below.

(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 laminate manufacturing method of the present invention, or the electronic device manufacturing method 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 polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors.

<Photosensitive compound>
Preferably, the photosensitive compound comprises a first photosensitive compound sensitive to the first wavelength and a second photosensitive compound sensitive to the second wavelength.
The photosensitive compound comprises a first photosensitive compound that is sensitive to the first wavelength and a second photosensitive compound that is sensitive to the second wavelength, whereby the photosensitive compound is sensitive to the first wavelength and the second wavelength. It is possible to form a photosensitive film that
In the above embodiment, the first photosensitive compound may or may not be sensitive to the second wavelength. Also, the second photosensitive compound may or may not be sensitive to the first wavelength.
Further, the photosensitive compound is a photosensitive compound that is sensitized in the exposure step (e.g., the first photosensitive compound and the second photosensitive compound described above), and further a photosensitive compound that is sensitized in the post-development exposure step. may contain.
The photosensitive compound that is sensitized in the post-development exposure step is preferably a photosensitive compound that is not sensitized in the exposure step but is sensitized in the post-development exposure step.

Whether or not a photosensitive compound is sensitive to light of a certain wavelength is determined by the following method.
A photosensitive compound and polymethyl methacrylate (PMMA) are dissolved in methyl ethyl ketone to prepare a composition for forming a model film. The content of the photosensitive compound with respect to the total mass of the photosensitive compound and PMMA in the model film-forming composition is 0.5 mmol/g. In addition, the amount of methyl ethyl ketone to be used with respect to the total mass of the photosensitive compound and PMMA in the model film-forming composition may be appropriately set according to the film thickness of the model film, which will be 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 mass ratio of and to the content is the same.
Moreover, the weight average molecular weight of PMMA shall be 10,000.
After that, the obtained composition for forming a model film is applied on glass and thermally dried at 80° C. for 1 minute to obtain a model film. The film thickness of the model film is set to 10 μm. After that, using the same light source as in the first exposure or the second exposure in the exposure step, the composition film is exposed with the same wavelength and dose as the exposure in the first exposure or the second exposure.
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 in the above solution by HPLC (high performance liquid chromatography).
Residual rate of photosensitive compound (%)=Content (mol) of photosensitive compound contained in model film after exposure/Content (mol) of photosensitive compound contained in model film before exposure×100
Further, when the residual ratio of the photosensitive compound is less than 80%, it is determined that the photosensitive compound is a compound sensitive to the first wavelength or the second wavelength. The residual rate is preferably 70% or less, more preferably 60% or less, and even more 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 does not react with the first wavelength or the second wavelength. The residual rate is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. The upper limit of the residual rate is not particularly limited, and may be 100%.

Moreover, it is preferable that the first photosensitive compound and the second photosensitive compound have different maximum absorption wavelengths. The difference in 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 even more preferably 20 nm or more.
The maximum absorption wavelength of a photosensitive compound is defined as the wavelength on the longest wavelength side among 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, 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 405nm are included as photosensitive compounds. Examples include a mode in which a 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 sensitive to the first wavelength and the second wavelength.
Furthermore, it is also one of preferred 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. A photosensitive film can be formed that is sensitive to two wavelengths.

The photosensitive compound is a compound that undergoes chemical changes such as generating radicals, acids, and bases during the exposure process, and that changes the solubility of the photosensitive film in the developer along with the structural changes. is preferred, and a compound that generates radicals in the exposure process is more preferred.
Moreover, the photosensitive compound is preferably a photopolymerization initiator, a photoacid generator, or a photobase generator.
When the photosensitive compound comprises a first photosensitive compound sensitive to light at a first wavelength and a second photosensitive compound sensitive to light at a second wavelength, the first photosensitive compound and the second photosensitive compound Although the compound may be of a different category than the compound, it is preferably a compound of the same category.
The above-mentioned compounds of different categories refer to, for example, an embodiment in which the first photosensitive compound is a photopolymerization initiator and the second photosensitive compound is a photoacid generator.
The compound of the same category is, for example, the first photosensitive compound is a photopolymerization initiator, the second photosensitive compound is also a photopolymerization initiator, the first photosensitive compound is An embodiment 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 It refers to an embodiment that is an agent.
Among these, both the first photosensitive compound and the second photosensitive compound are preferably photopolymerization initiators, more preferably photoradical polymerization initiators.

[Photopolymerization initiator]
Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.
A radical photopolymerization initiator is a compound that generates radicals in an exposure process.

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

The radical photopolymerization initiator is a compound having a molar extinction coefficient of at least about 50 L·mol ⁻¹ cm ⁻¹ with respect to light having a wavelength within the range of approximately 300 to 800 nm (preferably 330 to 500 nm). It is preferable to contain 1 type. The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the radical photopolymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. mentioned. For details thereof, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, and the contents thereof are incorporated herein.

Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

Hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can also be used.

Hydroxyacetophenone initiators include 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, Omnirad 1173, and Omnirad. 2959 and Omnirad 127 (trade name: both manufactured by IGM Resins).

As aminoacetophenone-based initiators, 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, which has a maximum absorption wavelength matched to a wavelength light source such as 365 nm or 405 nm, can also be used.

Acylphosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Also, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF), Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins) can be used.

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

As the radical photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator. An oxime compound that 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 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP-A-2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

It is also possible to use oxime compounds having fluorine atoms. Specific examples of such oxime compounds 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 compound (C-3) described in paragraph 0101 of JP-A-164471.

The most preferable oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.

More preferred radical photopolymerization 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. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, more preferably metallocene compounds or oxime compounds, and oxime compounds. is even more preferred.

Further, the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc. quinones condensed with the aromatic ring of , benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. A compound represented by the following formula (I) can also be used.

In formula (I), R ¹⁰⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms; a phenyl group substituted with at least one of an alkyl group of 18 and an alkyl group having 1 to 4 carbon atoms, or biphenyl, and R ^I01 is a group represented by formula (II) or the same as R ^I00 and each of R ¹⁰² to R ¹⁰⁴ is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or halogen.

In the formula, R ¹⁰⁵ to R ¹⁰⁷ are the same as R ¹⁰² to R ¹⁰⁴ in formula (I) above.

Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used.

When the photosensitive resin composition contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator is 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, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. Only one type of radical photopolymerization initiator may be contained, or two or more types may be contained. When two or more radical photopolymerization initiators are contained, the total is preferably within the above range.

[Photoacid generator]
The photosensitive resin composition of the present invention preferably contains a photoacid generator as a photosensitive compound.
By containing a photoacid generator, for example, an acid is generated in the exposed portion of the photosensitive film, the solubility of the exposed portion in the developer (for example, alkaline aqueous solution) increases, and the exposed portion is removed by the developer. 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 acid generated in the exposed area accelerates the cross-linking reaction of the cross-linking agent, and the exposed area becomes the non-exposed area. It is also possible to adopt a mode in which it is more difficult to be removed by a developer than the above. According to such an aspect, a negative relief pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid upon exposure, and includes quinonediazide compounds, diazonium salts, phosphonium salts, sulfonium salts, onium salt compounds such as iodonium salts, imidosulfonates, and oximes. Sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate can be used.

The quinonediazide compound includes a polyhydroxy compound in which the sulfonic acid of quinonediazide is ester-bonded, a polyamino compound in which the sulfonic acid of quinonediazide is sulfonamide-bonded, and a polyhydroxypolyamino compound in which the sulfonic acid of quinonediazide is ester-bonded and sulfonamide-bonded. and those bound by at least one of 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, both 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group are preferably used as quinonediazide. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. A 5-naphthoquinonediazide sulfonyl 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-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinone diazidesulfonyl group and a 5-naphthoquinone diazidesulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazidesulfonyl ester compound and a 5-naphthoquinone diazidesulfonyl ester compound may be contained. may contain.

The naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity and film retention rate are further improved.

Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
In addition, you may use a commercial item as a photo-acid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (all from Fujifilm Kojunyaku Co., Ltd.), Omnicat 250, Omnicat 270 (all of IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all of BASF).

When a photoacid generator is included, its content 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. is more preferable, and 2 to 15% by mass is even more 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 within 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 to be described later, for example, the base generated in the exposed area accelerates the cyclization of the specific resin, thereby promoting the cross-linking reaction of the cross-linking agent. It is also possible to adopt an aspect in which the exposed portion is more difficult to be removed by the developer than the non-exposed portion. According to such an aspect, a negative relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base upon exposure, and known ones can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, Kobunshi Kako, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A.; Sarker, andD. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M.; Shirai, and M. Tsunooka, J.; Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J.; Photopolym. Sci. Technol. , 3, 419 (1990); Tsunooka, H.; Tachi, and S.; Yoshitaka, J.; Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H.; Araki, M.; Shirai, J.; Photopolym. Sci. Technol. , 19, 81 (2006), transition metal compound complexes, those having a structure such as an ammonium salt, and those in which the amidine moiety is made latent by forming a salt with a carboxylic acid, Ionic compounds in which the base component is neutralized by forming a salt, and nonionic compounds in which the base component is made latent by urethane bonds and oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. can be mentioned.
In the present invention, more preferred examples of the photobase generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

The basic substance generated from the photobase generator is not particularly limited, but includes compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization rate, the basic substance preferably has a conjugate acid with a high pKa in DMSO (dimethylsulfoxide). The pKa is preferably 1 or more, more preferably 3 or more. Although the upper limit of the pKa is not particularly limited, it is preferably 20 or less.
Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa software (manufactured by ACD/Labs) is used as the pKa.

From the viewpoint of the storage stability of the photosensitive resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in its structure. Preferably there is no charge on it. As a photobase generator, the generated base is preferably latent using a covalent bond. It is preferable that a base is generated by reaction. If the photobase generator does not contain a salt in its structure, the photobase generator can be made neutral, so that the solvent solubility is better and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Moreover, from the viewpoint of the chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in its structure.

In addition, for the above reasons, the photobase generator preferably has a latent base generated as described above using a covalent bond, and the base generated has an amide bond, a carbamate bond, or an oxime bond. It is preferably latent using
Examples of the photobase generator according to the present invention include photobase generators having a cinnamic acid amide structure as disclosed in JP-A-2009-080452 and WO 2009/123122, and JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, carbamoyl Examples include photobase generators having an oxime structure, but are not limited to these, and other known photobase generator structures can be used.

In addition, as the photobase generator, compounds described in paragraph numbers 0185 to 0188, 0199 to 0200 and 0202 of JP-A-2012-093746, compounds described in paragraph numbers 0022 to 0069 of JP-A-2013-194205 , the compounds described in paragraphs 0026 to 0074 of JP-A-2013-204019, and the compounds described in paragraph 0052 of WO 2010/064631.

In addition, you may use a commercial item as a photobase generator. Commercial 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 ( manufactured by Tokyo Kasei Kogyo Co., Ltd.) and the like.

When a photobase generator is included, its content 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. is more preferable, and 2 to 15% by mass is even more 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 within 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 polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
Moreover, it is preferable that the specific resin 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 cross-linking agent. More preferably, it contains a photoradical polymerization initiator, a radical cross-linking agent, and a sensitizer as a photosensitizer. For example, a negative photosensitive layer is formed from such a photosensitive resin composition.
Moreover, the specific resin may have a polarity conversion 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 a photosensitizer. From such a photosensitive resin composition, for example, a chemically amplified positive photosensitive layer or negative 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]
Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
Formula (2)

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

A ¹ and A ² in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups 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 is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. A group represented by -Ar-L-Ar- is exemplified as a particularly preferred embodiment of the present invention. However, Ar is each independently an aromatic group, 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. Preferred ranges for these are as described above.

R ¹¹¹ is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, 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 It is preferably a diamine containing, more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. 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 a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O) -, -S-, -SO ₂ -, NHCO-, or preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms optionally 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 preferred.
In the formula, * represents a binding site with other structures.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; ,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′-diaminoparaterphenyl, 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'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-a aminophenyl)benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminooctafluorobiphenyl, 2,2-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3 ,3′,4,4′-tetraaminobiphenyl, 3,3′,4,4′-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4 '-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4, 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, 4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, Diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)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)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2 -bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino -at least one diamine selected from 2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolyzine and 4,4'-diaminoquaterphenyl is mentioned.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017/038598.

R ¹¹¹ is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film. However, Ar is each independently an aromatic group, 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 preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or SO ₂ -. 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。 From the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or (61). In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoro is a methyl group.
The monovalent organic groups represented by R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group.
Diamine compounds that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′- bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. 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 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 (6) is more preferable.
In formula (5) or (6), * represents a binding site with another structure.
Formula (5)

In formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, and NHCO-, and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -CO It is more preferably a group selected from -, -S- and SO ₂ -, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO It is more preferably a divalent group selected from the group consisting of -, -S- and SO ₂ -.

Formula (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。 Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds thereof may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Formula (O)

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is synonymous with R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 ,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2, 3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these C1-6 alkyl and C1-6 alkoxy derivatives are included.

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes residues of bisaminophenol derivatives.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, preferably at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, more preferably both contain a polymerizable group preferable. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group. 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, an amino groups. A group having an ethylenically unsaturated bond is preferable as the radically polymerizable group possessed by the polyimide precursor or the like.
The group having an ethylenically unsaturated bond includes 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), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
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-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group. , —CH ₂ CH(OH)CH ₂ —, and polyalkyleneoxy groups, and more preferably ethylene, propylene, trimethylene, —CH ₂ CH(OH)CH ₂ —, and polyalkyleneoxy groups. A polyalkyleneoxy group is more preferable from the viewpoint of easily satisfying formula (1) or formula (2) in .
In the present invention, a 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 multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in 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 preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylene A group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred aspects of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Monovalent organic groups include aromatic groups and aralkyl groups having an acidic group attached to one, two or three, preferably one, of the carbon atoms constituting the aryl group. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group.
More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms in the alkyl group is preferably 1-30. Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , isopropyl 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 group ) ethoxy groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. are mentioned. Among them, a cyclohexyl group is most preferable from the viewpoint of compatibility with high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group, which will be described later, is preferable.
Specific examples of aromatic groups include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene ring. ring, naphthacene 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, indolizine ring , indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or phenazine ring. A benzene ring is most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom, or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good. Examples of such tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.

At least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, an acetal group is more preferred.
Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

Also, the polyimide precursor preferably has a fluorine atom in its structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

For the purpose of improving 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 formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors and the like used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By adopting such a structure, it is possible to further widen the width of the exposure latitude.
Formula (2-A)

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represents 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 both are preferably polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently synonymous with 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 definition as R ¹¹² in Formula (5), and the preferred range is also the same.

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

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, still more preferably 22,000 to 25,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The polyimide precursor preferably has a molecular weight distribution of 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. Although the upper limit of the polyimide precursor molecular weight dispersity is not particularly defined, for example, it is preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, and even more preferably 3.2 or less. It is preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.
In the present specification, the molecular weight dispersity 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 soluble in a developer containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide refers to a polyimide that dissolves in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C. by 0.1 g or more, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
As used herein, the term "main chain" refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to the other linking chain.

- fluorine atom -
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a fluorine atom.
A fluorine atom is preferably included in, for example, R ¹³² in a repeating unit represented by formula (4) described later or R ¹³¹ in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R ¹³² in the repeating unit represented by 4) or R ¹³¹ in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of 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 resulting organic film, the polyimide preferably has silicon atoms.
A silicon atom, for example, is preferably contained in R ¹³¹ in a repeating unit represented by formula (4) described later, and R ¹³¹ in a repeating unit represented by formula (4) described later is an organic modified (poly ) is more preferably contained as a siloxane structure.
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 relative to the total mass of polyimide is preferably 0.01 to 5 mol/g, more preferably 0.05 to 1 mol/g.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R ¹³² in a repeating unit represented by the formula (4) described later, or R ¹³¹ in a repeating unit represented by the formula (4) described later. It is more preferably included as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by (4) or R ¹³¹ in the repeating unit represented by formula (4) described below.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and ethylene is contained in R ¹³¹ in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
The group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples 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, preferably a methyl group.

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 number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined.

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 one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).

In 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 combined, and X represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ● represents a bonding site with the oxygen atom to which R ²⁰¹ in formula (III) bonds.
In formulas (R1) to (R3), a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R ²¹ having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) is, 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 (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.

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

The amount of ethylenically unsaturated bonds relative to the total weight 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 crosslinkable groups other than ethylenically unsaturated bonds.
Examples of crosslinkable groups other than ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.
A crosslinkable group other than an ethylenically unsaturated bond is preferably included in, for example, R ¹³¹ in a repeating unit represented by formula (4) described later.
The amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total weight of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

-Polarity conversion group-
The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in formula (2) above, and preferred embodiments are also the same.

- Acid value -
When polyimide is subjected to alkali development, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable.
Also, 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.
Further, when the polyimide is subjected to development using a developer 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 preferred, and 5 to 20 mgKOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
Considering the dissociation reaction in which hydrogen ions are released from an acid, the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka.
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, more preferably a phenolic hydroxy group.

-Phenolic hydroxy group-
The polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
The polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably contained in, for example, R ¹³² in a repeating unit represented by formula (4) described later or R ¹³¹ in a repeating unit represented by formula (4) described later.
The amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 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 it preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4) A compound containing a repeating unit and having a polymerizable group is more preferable.
Formula (4)

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When it has a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in
Formula (4-1)

In formula (4-1), R ¹³³ is a polymerizable group, and other groups are the same as in formula (4).
Formula (4-2)

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).

The polymerizable group is synonymous with the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group are the same as those of R ¹¹¹ in formula (2), and the preferred range is also the same.
R ¹³¹ also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in its main chain from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferably a diamine residue containing no aromatic ring.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group are the same as those for R ¹¹⁵ in formula (2), and the preferred range is also the same.
For example, four bonds of a tetravalent organic group exemplified as R ¹¹⁵ combine with four —C(═O)— moieties in the above formula (4) to form a condensed ring.

Further, R ¹³² includes a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. A specific example is the example of R ¹¹⁵ in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

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

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

For the purpose of improving 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.

In addition, in order to improve the storage stability of the composition, the main chain end of the polyimide may be blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, or the like. preferable. Among these, it is more preferable to use monoamines, and preferred monoamine compounds include 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-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 terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidation 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, insulating properties, etc. of the resulting 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, for example, by the method described below.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C. for 1 hour, the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula.
Imidation rate (%) = (peak intensity P1/peak intensity P2) x 100

The polyimide may contain repeating structural units of the above formula (4) that all contain 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 contain a repeating unit of The polyimide may also contain other types of repeating structural units in addition to the repeating units of formula (4) above.

For polyimide, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid A method of reacting a diamine compound with a diamine compound, a method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a monoactive ester compound, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent with a tetracarboxylic dianhydride and an alcohol to obtain a diester, then acid chloride the remaining dicarboxylic acid, diamine (a part of which is a monoamine Substitution with a terminal blocking agent) is used to obtain a polyimide precursor, which is completely imidized using a known imidization reaction method, or imide in the middle Synthesis using a method of stopping the polymerization reaction and partially introducing an imide structure, or a method of partially introducing an imide 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, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film 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. Moreover, when two or more types of polyimide are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is within 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]
Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
Formula (3)

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

In formula (3), R ¹²³ and R ¹²⁴ each have the same meaning as R ¹¹³ in formula (2), and the preferred ranges are 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 preferred. As the aliphatic group, a linear aliphatic group is preferred. 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 residue 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.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing linear aliphatic groups 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, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, thoria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

（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。）

(Wherein, 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, the following dicarboxylic acids having aromatic groups are preferred, and dicarboxylic acids consisting of only the following aromatic groups and two —COOH are more preferred.

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。

wherein 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 * independently represents a binding site to another structure.

Specific examples of dicarboxylic acids containing aromatic groups 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 preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. -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'-diamino-4, 4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination.

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

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 # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. R ¹²² is also preferably a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the total four * and # are binding sites with the nitrogen atom to which R ¹²² in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R ¹²² in formula (3) binds, or two * are binding sites to the nitrogen atom to which R ¹²² in formula (3) binds and two #s are more preferably a binding site to the oxygen atom to which R ¹²² in formula (3) binds, and two * are the oxygen to which R ¹²² in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R ¹²² in formula (3) is bonded.

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc). _R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom _, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or 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 formula (A-sc), * indicates binding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (A-s), the ortho position of the phenolic hydroxyl group, that is, having a substituent also at R ₃ is thought to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and 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 (A-s), when R ₂ is an alkyl group and R ₃ is an alkyl group, high transparency to the i-line and high cyclization rate when cured at a low temperature are said to be obtained. It is preferable because the effect can be maintained.

Further, in formula (As) above, it is more preferred that R ₁ is alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene for R ₁ include linear or branched alkylene groups having 1 to 8 carbon atoms, among which —CH ₂ —, —CH(CH ₃ )-, -C(CH ₃ ) ₂ - have sufficient solubility in solvents while maintaining the effects of high transparency to i-line 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 bisaminophenol derivative represented by the above formula (A-s), for example, refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506. , the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, the contents of which are incorporated herein. incorporated into. Of course, it goes without saying that they are not limited to these.

The polybenzoxazole precursor may also contain other types of repeating structural units in addition to the repeating units of formula (3) above.
It is preferable to contain a diamine residue represented by the following formula (SL) as another type of repeating structural unit from the viewpoint of suppressing the occurrence of warping due to ring closure.

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. 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. Polymerization of a structure and b structure may be block polymerization or random polymerization. The mol % of the Z moiety is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.

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

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor, for example, when used in the composition described later, is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further Preferably it is 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, 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]
Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group. As the polymerizable group, a radically polymerizable group is preferred. Further, it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.

In Formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
In the case of having a polar conversion group such as a polymerizable group or an acid-decomposable group, the polar conversion group such as a polymerizable group or an acid-decomposable group may be located on at least one of R ¹³³ and R ¹³⁴ . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
Formula (X-1)

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polar conversion group such as a polymerizable group or an acid-decomposable group. It is an organic group, and other groups are as defined in formula (X).
Formula (X-2)

In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups are the same as in formula (X).

The polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described above for the polymerizable group possessed by the polyimide precursor or the like.

R ¹³³ represents a divalent organic group. Divalent organic groups include aliphatic or aromatic groups. A specific example is the example of R ¹²¹ in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of ^R121 .

R ¹³⁴ represents a tetravalent organic group. Tetravalent organic groups include examples of R ¹²² in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of ^R122 .
For example, four bonds of a tetravalent organic group exemplified as R ¹²² combine with the nitrogen atom and 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 structure below. Each * independently represents a binding site with another structure.

Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when the film is oxazolized by heating can be reduced, and the occurrence of warpage can be more effectively suppressed.

The polybenzoxazole may contain repeating structural units of the above formula (X) that all contain one type of R ¹³¹ or R ¹³² , and the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² It may contain a repeating unit of X). Moreover, the polybenzoxazole may also contain other types of repeating structural units in addition to the repeating units of the above formula (X).

Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
In the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield.

The weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film 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. Moreover, 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 within the above range.

[Method for producing 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, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using 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 halogenating agent. As the non-halogen catalyst, known amidation catalysts containing no halogen atoms can be used without particular limitation. Examples include salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
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, promoting the cyclization reaction by acting a catalyst), or directly , polyimide may be synthesized.

-Terminal blocking agent-
In the production method of polyimide precursors, etc., in order to further improve the storage stability, terminal blockers such as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds are used to block the ends of polyimide precursors. Sealing is preferred. As the terminal blocker, it is more preferable to use a monoamine, and preferred monoamine compounds include 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- aminobenzenesulfonic 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. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Solid precipitation-
A step of depositing 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 can be precipitated in water and then dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor or the like is soluble, thereby allowing solid deposition.
Thereafter, the polyimide precursor or the like is 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 relative to the total solid content of the composition. More preferably, it is more preferably 50% by mass or more. Further, 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, relative to the total solid content of the composition. 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 types are included, the total amount is preferably within the above range.

<Other resins>
The composition of the present invention may further contain other resins (hereinafter also simply referred to as "other resins") different from the specific resins, in addition to the specific resins described above.
Other resins include polyamideimides, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, acrylic resins, and the like.
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, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, by adding an acrylic resin having a high polymerizable group value having a weight average molecular weight of 20,000 or less to the composition, the composition It is possible to improve the applicability of the material, the solvent resistance of the organic film, and the like.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the composition. more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more .
In addition, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass, based on the total solid content of the composition. It is more preferably 60% by mass or less, and even more preferably 50% by mass or less.
In addition, as a preferred embodiment of the composition of the present invention, the content of other resins may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, relative to the total solid content of the composition. More preferably, it is 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited as long as it is 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 types are included, the total amount is preferably within the above range.

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

Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone , δ-valerolactone, alkyl alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropion methyl acid and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvate Suitable examples include propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.

Ethers such as 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 Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

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

Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.

Suitable sulfoxides include, for example, dimethyl sulfoxide.

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

From the viewpoint of improving the properties of the coating surface, it is also preferable to mix two or more solvents.

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- 1 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 composed of two or more solvents A mixed solvent is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

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

Only one kind of solvent may be contained, or two or more kinds may be contained. When two or more solvents are contained, the total is preferably within 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 that promotes a bonding reaction with other groups upon exposure of the photosensitive compound in the above exposure step.
Cross-linking agents include radical cross-linking agents or other cross-linking agents.

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

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

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 (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like. As specific examples, paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

The radical cross-linking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin and trimethylolethane. Compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated are described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates such as those described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490, polyester acrylates, epoxy resins and (meth)acryl Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, and mixtures thereof can be mentioned. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.

Further, as preferred radical cross-linking agents other than those described above, JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.

Furthermore, other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493. vinyl phosphonic acid compounds and the like can also be mentioned. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, the journal of Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964, compounds described in paragraphs 0087 to 0131 of WO 2015/199219 can also be preferably used, the contents of which are herein incorporated into the book.

Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, which are described together with specific examples as formulas (1) and (2) in JP-A-10-062986, It can be used as a radical cross-linking agent.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, the contents of which are incorporated herein.

As a radical cross-linking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. ), A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) ) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth)acryloyl groups via ethylene glycol residues or propylene glycol residues Structures that are linked together are preferred. These oligomeric types can also be used.

Examples of commercially available radical cross-linking agents include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation), etc. mentioned.

Examples of radical cross-linking agents include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Furthermore, as a radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also

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. A radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable. Particularly preferably, in a radical cross-linking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound 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 polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.

The acid value of the radical cross-linking agent having acid groups is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.

In the photosensitive resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as a radical cross-linking agent from the viewpoint of suppressing warpage associated with pattern elastic modulus control. Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) 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 allyl glycidyl 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 a radical cross-linking agent is contained, its content 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. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

One type of radical crosslinking agent may be used alone, or two or more types may be mixed and used. When two or more are used in combination, the total amount is preferably within 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-described radical cross-linking agent, and covalently bonds with other compounds or reaction products thereof in the composition by exposure of the above-described photosensitive compound. is preferably a compound having a plurality of groups in the molecule that promote the reaction to form a reaction that forms a covalent bond with other compounds in the composition or its reaction product is an acid or base Compounds having a plurality of functionally promoted groups in the molecule are preferred.
The acid or base is an acid or base generated from a photoacid generator or photobase generator, which is a photosensitive compound, in the exposure step.
As other cross-linking agents, compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups are preferred, and at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is a nitrogen atom. Compounds having structures directly bonded to are more preferred.
Other cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with a methylol group or an alkoxymethyl group. Compounds with substituted structures are included. The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
As the amino group-containing compound, a melamine-based crosslinking agent is a melamine-based crosslinking agent, a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent, and an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent. A cross-linking agent using 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 urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of system cross-linking agents.

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

Specific examples of urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycoluril. , trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, di propoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril, etc. a glycoluril-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 ethylene urea-based cross-linking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxymethyl ethylene urea;
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy propylene urea-based cross-linking agents such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like.

Specific examples of benzoguanamine-based cross-linking agents 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.

Other compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups include at least one group selected from the group consisting of methylol groups and alkoxymethyl groups on an aromatic ring (preferably a benzene ring). Compounds in which groups are directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4′,4″-ethylidene tris[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.

Commercial products may be used as other cross-linking agents, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals 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 (Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, hereinafter the same) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) ) and the like.

Also, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds 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 less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the photosensitive resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus is further lowered, and warping 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 2-15.

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. , alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade names, manufactured by ADEKA Corporation), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Serbinase B0134, B0177 ( The above trade names, 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 (both trade names, manufactured by Nippon Kayaku Co., Ltd.) and the like.

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

[Benzoxazine compound (compound having a benzoxazolyl group)]
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress warpage.

Preferable examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac dihydrobenzoxazine oxazine compounds. 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, More preferably 0.5 to 15% by mass, particularly preferably 1.0 to 10% by mass. Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-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) ) naphtho(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-2016-027357 can be referred to, the contents of which are incorporated herein.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is 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 from 0.1 to 15% by mass, and even more preferably from 0.5 to 10% by mass. The sensitizers may be used singly or in combination of two or more.

<Thermal polymerization initiator>
The photosensitive resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a 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 advanced, so the chemical resistance can be further improved.

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

When a thermal polymerization initiator is included, its content 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. One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

<Thermal acid generator>
The photosensitive resin composition of the present invention may contain a thermal acid generator.
For example, when the pattern forming method of the present invention includes a heating step, the thermal acid generator is a compound that 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 accelerating the cross-linking reaction of at least one compound selected from oxazine compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, no acid is generated during drying (prebaking: about 70 to 140° C.) after the composition is applied to the substrate, and the final heating (curing: 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 initiation temperature is obtained as the lowest exothermic peak temperature when the thermal acid generator is heated up to 500° C. in a pressure-resistant capsule at 5° C./min.
Equipment used for measuring the thermal decomposition initiation temperature includes Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and trifluoromethane. Haloalkyl sulfonic acids, such as sulfonic acids, and the like are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, those that generate C 1-4 alkylsulfonic acids and C 1-4 haloalkylsulfonic acids are more preferable, and methanesulfonic acid. (4-hydroxyphenyl)dimethylsulfonium, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl methanesulfonate (4-((methoxy carbonyl)oxy)phenyl)methylsulfonium, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, (4- ((Methoxycarbonyl)oxy)phenyl)dimethylsulfonium, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl) Propanenitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane, is preferred as the thermal acid generator.

Further, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferable as thermal acid generators.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts 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. From the viewpoint of electrical insulation of the organic film, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Onium salt>
The compositions of the invention preferably contain an onium salt.
In particular, when a polyimide precursor is included as the specific resin, the composition preferably includes an onium salt.
Although the type of onium salt is not particularly limited, ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts are preferred.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

In addition, an onium salt is a salt of a cation having an onium structure and an anion, and the cation and anion may be bonded via a covalent bond or may not be bonded via a covalent bond. .
That is, the onium salt may be an intramolecular salt having a cation part and an anion part 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 an intermolecular salt is preferred. Moreover, in the composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded or dissociated by ionic bonding.
The cations in the onium salt are preferably ammonium cations, pyridinium cations, sulfonium cations, iodonium cations or phosphonium cations, and more preferably at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and iodonium cations.

The onium salt used in the present invention may be a thermal base generator.
A thermal base generator is a compound that generates a base when heated, and includes, for example, acidic compounds that generate a base when heated to 40° C. or higher.
Onium salts include, for example, onium salts described in paragraphs 0122 to 0138 of WO 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 based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, still more 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, still more preferably 20% by mass or less, even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.
One or two or more onium salts can be used. When two or more kinds are used, the total amount is preferably within the above range.

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

In Formula (B1) and Formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. Also, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this 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, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.

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

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

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

The compound represented by Formula (B1) is preferably a compound represented by Formula (B1-1) or Formula (B1-2) below.

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are respectively the same as Rb ¹ and Rb ² in formula (B1).
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

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

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more 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 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.

The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same definitions as Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more 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 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, 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, specific examples of compounds that are thermal base generators or specific examples of other thermal base generators include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within 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 becomes possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the photosensitive film.

Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole are preferably used.

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

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compounds described in paragraph 0166 of WO 2015/199219, and the like can be used.

Specific examples of migration inhibitors 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 0 It is more preferably from 0.05 to 2.0% by mass, and even more preferably from 0.1 to 1.0% by mass.

Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.

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

Polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, 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, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

Also, 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 is 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. is preferred, 0.02 to 3 mass % is more preferred, and 0.05 to 2.5 mass % is even more preferred.

One type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

<Metal adhesion improver>
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like. A silane coupling agent etc. are mentioned as a metal adhesion improving agent.

Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992. Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055 are included. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the formulas below, Et represents an ethyl group.

Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used. .

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the specific resin. 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 improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

<Other additives>
The photosensitive resin composition of the present invention may contain various additives such as surfactants, chain transfer agents, higher fatty acid derivatives, inorganic particles, curing agents, Curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. 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]
Various types of surfactants may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various kinds of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used. The following surfactants are also preferred. In the following formula, the parenthesis indicating the repeating unit of the main chain indicates the content (mol %) of each repeating unit, and the parenthesis indicating the repeating unit of the side chain indicates the repeating number of each repeating unit.

In addition, surfactants can also be used compounds described in paragraphs 0159 to 0165 of WO 2015/199219.

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 with respect to the total solid content of the photosensitive resin composition of the present invention. preferably 0.005 to 1.0% by mass. One type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably within the above range.

[Chain transfer agent]
The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Jiten, 3rd edition (edited by Kobunshi Gakkai, 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 either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent can also use compounds described in paragraphs 0152 to 0153 of WO 2015/199219.

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. It is preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.

[Higher Fatty Acid Derivative]
In the photosensitive resin composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. It may be unevenly distributed on the surface of the object.

Moreover, the higher fatty acid derivative can also use the compound of the paragraph 0155 of international publication 2015/199219.

When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. is preferred. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within 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 coated surface properties. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container.

From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When multiple metals are included, the total of these metals is preferably within the above range.

In addition, 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. Examples include methods such as performing filter filtration on the raw materials constituting the photosensitive resin composition of the invention, and lining the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible. be able to.

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

Conventionally known containers can be used as the container for the photosensitive resin composition of the present invention. In addition, for the storage container, for the purpose of suppressing the contamination of the raw material and the photosensitive resin composition, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 7 types of 6 types of resin are used. It is also preferred to use a layered bottle. Examples of such a container include the container described in JP-A-2015-123351.

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

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

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the photosensitive resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When pressurizing and filtering, the pressure to pressurize 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. You may combine filter filtration and the impurity removal process using an adsorbent. A known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

EXAMPLES The present invention will be described more specifically with reference to examples below. Materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Synthesis Example 1: Synthesis of polymer A-1>
9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride, oxydiphthalic dianhydride, while removing water in a dry reactor equipped with a stirrer, condenser and flat-bottomed joint fitted with an internal thermometer. 10.0 g (32.25 mmol) of the product were 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. After cooling the mixture to -20°C, 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 and stirred for 2 hours before adding 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. To the resulting clear solution was then added 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP dropwise 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 speed 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 resulting 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 were removed while removing water in a dry reactor equipped with a stirrer, condenser and a flat-bottomed joint fitted with an 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 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 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 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 further stirred 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, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio) and stirred for 30 minutes at a speed of 2,000 rpm. The precipitated polyimide resin was collected by filtration, spray-washed with 1.5 liters of water, and then mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The resulting 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.) was placed in a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube. 64.28 g of N-methyl-2-pyrrolidone (NMP) were added and 38.07 g (0.320 mol) of thionyl chloride were added dropwise at room temperature. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and excess thionyl chloride was distilled off under reduced pressure to obtain 1,4-cyclohexanedicarboxylic acid dichloride (cis-, trans-mixture) as a 30 wt% NMP solution. rice field.
73.25 g (0.200 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane (Bis-AP -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 with a dry ice/methanol bath. To this solution was added 30.11 g (0.144 mol) of 1,4-cyclohexanedicarboxylic acid dichloride in 30% by weight NMP solution and 3.83 g (0.14 mol) of 1,4-cyclohexanedicarboxylic acid dichloride in 30% by weight while maintaining the reaction temperature between -5°C and -15°C. 016 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 96.25 g of NMP were added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, the reaction solution was cooled to −5° C. or lower using 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.) was added. ) and 34.5 g of NMP was added dropwise. After the addition was complete, it was stirred for an additional 16 hours.
The reaction was diluted with 550 g of NMP and poured into 4 L of vigorously stirred deionized/methanol (80/20 by volume) mixture, the precipitated white powder was collected by filtration and washed with deionized water. . The polymer was dried under vacuum at 50° C. for 2 days to obtain resin A-1a.
25.00 g of Resin A-1a, 125 g of NMP and 125 g of methyl ethyl ketone were added to an eggplant flask and concentrated under reduced pressure at 60° C. until the content 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 (Fuji Film Wako Pure Chemical Co., Ltd. product) was added and stirred at room temperature for 1.5 hours. The obtained solution was diluted by adding 0.37 g of triethylamine and 150 g of NMP.
The resulting solution was poured into a vigorously stirred 2 L deionized water/methanol (80/20 volume ratio) mixture and the precipitated white powder was collected by filtration and washed with deionized water. The polymer was dried under vacuum at 50° C. for 2 days to obtain polymer A-3.

<Synthesis Example 4: Synthesis of polymer A-4>
In Synthesis Example 1, except that 6.82 g (58.7 mmol) of 1,6-diaminohexane was used in place of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether. A 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 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) are mixed and stirred at a temperature of 60° C. for 18 hours to give 4,4′-oxydiphthalic acid and A diester was prepared with 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10.degree. C. and 16.12 g (135.5 mmol) of _SOCl.sub.2 was added over 10 minutes while maintaining the temperature at -10.+-.4.degree. After dilution 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 overnight at room temperature. The polyimide precursor was then precipitated by adding 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed 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 by filtration again. Then, the resulting polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain 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. , dried over molecular sieves. 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.degree. C. and 16.12 g (135.5 mmol) of _SOCl.sub.2 was added over 10 minutes while maintaining the temperature at -10.+-.4.degree. Viscosity increased during SOCl ₂ addition. After dilution 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'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was then added to the reaction mixture over 20 minutes while maintaining the temperature between -5 and 0°C. Dripped. Then, the solution and the reaction mixture were allowed to react at 0° C. for 1 hour, then 70 g of ethanol was added, and the mixture was stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed 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. The resulting polyimide precursor was then 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. In Comparative Examples, the components shown in Table 2 below were mixed to obtain respective comparative compositions.
Specifically, the contents of the components described in Table 1 or Table 2 were set to the amounts described in "Parts by mass" in Table 1 or Table 2. In each composition, the solvent content was adjusted so that the solid content concentration (% by mass) of the composition was the value shown in Table 1 or Table 2.
The resulting photosensitive resin composition and comparative composition were pressure-filtered at a pressure of 0.3 MPa through a polytetrafluoroethylene filter having a filter pore size of 0.8 μm.
Also, in Table 1 or Table 2, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component described 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 examples

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

[Acid cross-linking agent]
・ B-4: Nikalac 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 Co., Ltd.)
· C-4: a photoacid generator represented by the following formula (C-4) (manufactured by BASF, PAG-103)

〔Silane coupling agent〕
・D-1: N-(3-(triethoxysilyl)propyl) phthalamic acid ・D-2: Benzophenone-3,3′-bis(N-(3-triethoxysilyl)propylamide)-4,4′ -Dicarboxylic acid D-3: IM-1000 (manufactured by JX Metals Co., Ltd.)
・ D-4: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu 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: ethyl 7-(diethylamino)coumarin-3-carboxylate F-3: 1H-tetrazole F-4: N-phenyl Diethanolamine F-5: 1,3-dibutylthiourea F-6: Megafac F-554 (manufactured by DIC Corporation)

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

[Thermal base generator]
· H-1: a compound described in 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 “Ratio in solvent” indicates the content (% by mass) of each solvent with respect to the total mass of the solvent.

<Evaluation>
[Evaluation of Pattern Formability]
- Formation of photosensitive film -
The photosensitive resin composition prepared in each example and comparative example or the comparative composition was spin-coated on a disk-shaped silicon wafer with a diameter of 200 mm ("A" was written in the column of "application method"). Examples) or by slit coating (examples with "B" in the "Method of Application" column).
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.
For spin coating, the number of rotations was adjusted so that the film thickness after drying would be the film thickness described in the "Film thickness (μm)" column of Table 1 or Table 2, and the coating was applied by rotating for 30 seconds. Regarding the slit coating, the distance between the substrate and the slit die is 200 μm, and the distance between the liquid discharge ports of the slit die is 150 μm. The amount of liquid discharged was adjusted so as to obtain a film thickness of .

-exposure-
In the example where "365" or the like is described in the "first exposure wavelength (nm)" column of Table 1 or Table 2, the laser light having the described wavelength is used as the light having the first wavelength. Exposure with light having one wavelength was performed. ,
In the example where "365 (H)" or the like is described in the "first exposure wavelength (nm)" column of Table 1 or Table 2, wavelengths other than the stated wavelength ± 10 µm are filtered by a band-pass filter. Using the cut high-pressure mercury lamp as light having the first wavelength, exposure was performed with light having the first wavelength.
In the example where "405" or the like is described in the column "Second exposure wavelength (nm)" in Table 1 or Table 2, the laser light having the described wavelength is used as the light having the second wavelength. Exposure with light having two wavelengths was performed. ,
In the example where "405 (H)" or the like is described in the "second exposure wavelength (nm)" column of Table 1 or Table 2, wavelengths other than the stated wavelength ± 10 µm are filtered by a band-pass filter. Using the cut high-pressure mercury lamp as light having the second wavelength, exposure was performed with light having the second wavelength.
In the examples described as "M" in the "exposure method" column of Table 1 or Table 2, exposure was performed using a binary mask having a 1:1 line and space pattern with a width of 20 μm as a photomask. . The irradiation amount (exposure amount) was adjusted so that the energy per unit area was equal in any light source.
In the examples 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 adjusted so that the energy per unit area was equal in any light source.
In the examples 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 simultaneously.
In the examples described as "B" in the "Timing" column of Table 1 or Table 2, the exposure with the light having the second exposure wavelength was performed after the start of the exposure with the light having the first exposure wavelength. The start of the exposure with light having the second exposure wavelength was taken as half the exposure time at the first exposure wavelength.
In the examples with "C" in the "Timing" column of Table 1 or Table 2, the exposure with the light with the second exposure wavelength was started immediately after the end of the exposure with the light with the first exposure wavelength.
In the example where "D" is entered in the "Timing" column of Table 1 or Table 2, the exposure with light having the second exposure wavelength is started 10 seconds after the end of the exposure with light having the first exposure wavelength. did.
In Comparative Example 1, since only exposure with light having the first exposure wavelength was performed, "-" is indicated in the "Timing" column.
In the example described as "A" in the "overlapping area" column of Table 1 or Table 2, the region (first region) exposed by light having the first exposure wavelength and the light having the second exposure wavelength Exposure was performed with the region exposed by (second region) 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 100%.
In the example in which "B" is written 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 to form a 20 µm wide area. : A region exposed to light having a first exposure wavelength using a binary mask on which a one line and space pattern is formed, and a region exposed to light having a second exposure wavelength (second region) is photo Using a binary mask formed with a 16:24 line-and-space pattern with a width of 16 μm as a mask, 2 μm from both ends of the first region is exposed as an unexposed region. and the area ratio of the overlapping portion of the second region was set to 80%.

-developing-
In the example described as "S" in the "developer" column of Table 1 or Table 2, the exposed photosensitive film (resin layer) was developed with cyclopentanone at 25 ° C. for 60 seconds, and a line with a width of 20 µm was developed. And-space patterns were formed. Then, in a nitrogen atmosphere, the temperature was raised at a temperature increase rate of 10 ° C./min, and after reaching the temperature described in the "Cure temperature (° C.)" column of Table 1 or Table 2, The temperature was maintained for the time described in the column of "curing time (min)" 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 treated with a 2.3% by 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 was raised at a temperature increase rate of 10 ° C./min, and after reaching the temperature described in the "Cure temperature (° C.)" column of Table 1 or Table 2, The temperature was maintained for the time described in the column of "curing time (min)" to form a pattern.
The formed pattern was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) to evaluate the presence or absence of pattern peeling. The cross section of the pattern was observed using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) to evaluate the presence or absence of undercut.
The pattern formability results obtained were evaluated according to the following evaluation criteria, and the evaluation results are shown in the "pattern formability" column of Table 1 or Table 2. It is preferable that pattern peeling is not recognized, and it is more preferable that neither pattern peeling nor undercut is recognized.
-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 undercutting were observed.

[Evaluation of chemical resistance]
- Calculation of dissolution rate -
In each example or comparative example, a photosensitive film was formed on a silicon wafer by the same method as the photosensitive film formation in the evaluation of pattern formability.
After that, in each example or comparative example using a resin composition or a comparative composition containing at least one of C-1 to C-3 as a photosensitive compound, the "exposure method" in Table 1 or Table 2 For the examples with "M" in the column, the entire surface of the photosensitive film was exposed without using a photomask. Except that laser exposure was applied to the entire surface of the photosensitive film, exposure was performed in the same manner as in the evaluation of the pattern formability described above to obtain a resin film.
In the examples using the resin composition containing C-4 as the photosensitive compound, the resin film was used as the photosensitive film without exposure.
Next, the resin film obtained in each example or comparative example was heated in a nitrogen atmosphere at a heating rate of 10° C./min. After reaching the indicated temperature, the temperature was maintained for the time indicated in the "curing 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.
Chemical: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The cured film was immersed in the chemical at 75°C for 15 minutes. The film 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 are shown 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 pattern peeling is suppressed in the pattern forming method of the present invention as compared with the pattern forming method according to Comparative Example 1 in which the exposure with light having the second wavelength is not performed.

<Example 101>
The photosensitive resin composition used in Example 1 is applied 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 with a thickness of 20 μm, it was exposed with a laser beam having a wavelength of 365 nm and a laser beam having a wavelength of 405 nm at an exposure amount of 400 mJ/cm ² . Exposure was performed through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 20 μm). After exposure, the film 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 rewiring layer. This interlayer insulating film for rewiring layer was excellent in insulating properties.
Further, when an electronic device was manufactured using the above interlayer insulating film for rewiring layer, it was confirmed that the device operated without any problem.

Claims (12)

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;
wherein said exposing step comprises exposing with light having a first wavelength and exposing 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,
At least a portion of a first region of the photosensitive film exposed to light having the first wavelength and a second region exposed to light having the second wavelength overlap,
The photosensitive resin composition contains a photosensitive compound and at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors ,
said photosensitive compound comprises a first photosensitive compound sensitive to said first wavelength and a second photosensitive compound sensitive to said second wavelength
Pattern formation method. 2. The pattern forming method according to claim 1 , wherein said first wavelength is 200 to 400 nm. 3. The pattern forming method according to claim 1, wherein said second wavelength is 300-500 nm. 4. The pattern forming method according to claim 1, 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 4 , wherein the developer used in the developing step is a developer containing an organic solvent. The pattern forming method according to any one of claims 1 to 5 , wherein the development in the developing step is negative development. 7. The pattern forming method according to claim 1, wherein the photosensitive film used in the exposure step has a thickness of 5 to 50 μm. The pattern forming method according to any one of claims 1 to 7 , 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 8 , wherein the resin is a polyimide precursor. The pattern forming method according to any one of claims 1 to 9 , wherein the photosensitive resin composition further contains a sensitizer. A method for producing a laminate, comprising the pattern forming method according to any one of claims 1 to 10 . An electronic device manufacturing method comprising the pattern forming method according to any one of claims 1 to 10 or the laminate manufacturing method according to claim 12.