JP7367049B2 - Pattern forming method, photosensitive resin composition, laminate manufacturing method, and semiconductor device manufacturing method - Google Patents

Description

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

Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulation properties, and are therefore used in a variety of applications. The above-mentioned uses are not particularly limited, but in the case of semiconductor devices for mounting, for example, patterns containing these resins may be used as materials for insulating films or 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 above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of photosensitive resin compositions containing these resins or their precursors.
By applying such a photosensitive resin composition to a base material, for example, by coating, etc., and then performing exposure, development, heating, etc. as necessary, a cured resin can be formed on the base material. .
Photosensitive resin compositions can be applied by known coating methods, so there are many manufacturing issues, such as a high degree of freedom in designing the shape, size, and application position of the photosensitive resin composition. It can be said that it has excellent adaptability. In addition to the high performance of polyimide, polybenzoxazole, etc., from the viewpoint of excellent manufacturing adaptability, there are increasing expectations for the industrial application and development of photosensitive resin compositions containing these resins.

For example, Patent Document 1 describes a photosensitive resin composition that is characterized in that a photosensitive resin composition comprising a polybenzoxazole precursor and diazoquinone is exposed and developed to create a pattern, and then the entire surface is further exposed and cured. Curing methods are described.

Japanese Patent Application Publication No. 9-146273

Conventionally, a photosensitive resin composition containing polyimide, polybenzoxazole, or a precursor thereof is applied to a base material, exposed and developed, and then heated as necessary to form a pattern. It's here.
In forming the above-mentioned patterns, it is desired to provide a pattern forming method that provides an excellent pattern shape.

The present invention relates to a pattern forming method with an excellent pattern shape, a photosensitive resin composition used in the pattern forming method, a method for producing a laminate including the pattern forming method, and an electronic device including the pattern forming method. The purpose of the present invention is to provide a method for manufacturing a device.

Examples of representative embodiments of the invention are shown below.
<1> A first area exposure step of selectively exposing a first area, which is a partial area of a photosensitive film made of a photosensitive resin composition,
a second region exposure step of selectively exposing a second region, which is a partial region of the photoresist film after the first region exposure step;
a developing step of developing the photoresist film after the second area exposure step;
At least a part of the area included in the first area and at least a part of the area included in the second area are common areas,
The photosensitive resin composition contains at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, and a photosensitizer.
Pattern formation method.
<2> A third region exposure step of selectively exposing a third region which is a part of the photoresist film after the second region exposure step, and a part of the photoresist film after the third region exposure step. The developing step is a step of developing the photoresist film after the fourth region exposing step, and the developing step is a step of developing the photoresist film after the fourth region exposing step, which is included in the third region. At least a part of the area is a common area with at least a part of the area included in any one of the first area, the second area, and the fourth area, and at least one area included in the fourth area is a common area. The pattern forming method according to <1>, wherein the part of the area and at least part of the area included in any one of the first area, the second area, and the third area are common areas.
<3> Among the steps of exposing a part of the photoresist film included before the development step, it is the time from the end of one exposing step to the start of another exposing step, The pattern forming method according to <1> or <2>, wherein the time period not including any other exposure step is 0.1 seconds or more.
<4> The pattern forming method according to any one of <1> to <3>, wherein the exposure wavelength in the first region exposure step and the second region exposure step is 300 to 450 nm.
<5> The pattern forming method according to any one of <1> to <4>, wherein the photosensitive film made of the photosensitive resin composition has a thickness of 10 μm or more.
<6> The pattern forming method according to any one of <1> to <5>, wherein the development in the development step is performed using an organic solvent as a developer.
<7> Any of <1> to <6>, wherein the ratio of the area of the area included in both the first region and the second region to the total area of the first region is 50% to 100%. The pattern forming method according to item 1.
<8> The pattern forming method according to any one of <1> to <7>, wherein the resin is a polyimide precursor.
<9> The pattern forming method according to any one of <1> to <8>, wherein the resin has a radically polymerizable group.
<10> The pattern forming method according to any one of <1> to <9>, wherein the photosensitive resin composition further contains a radical crosslinking agent.
<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> A method for manufacturing an electronic device, comprising the pattern forming method according to any one of <1> to <11> or the method for manufacturing a laminate according to <13>.

According to the present invention, there is provided a pattern forming method excellent in the shape of the resulting pattern, a photosensitive resin composition used in the pattern forming method, a method for manufacturing a laminate including the pattern forming method, and a method for producing a laminate including the pattern forming method. A method of manufacturing an electronic device is provided.

Main embodiments of the present invention will be described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range expressed using the symbol "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit, respectively.
As used herein, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.
In the description of a group (atomic group) in this specification, the description that does not indicate substitution or unsubstitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both "acrylate" and "methacrylate", or either "(meth)acrylate", 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 formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. Further, 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 this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement). In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and guard column HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, those molecular weights are measured using THF (tetrahydrofuran) as an eluent. Furthermore, unless otherwise specified, a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection in the GPC measurement.
In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", there is another layer above or below the reference layer among the plurality of layers of interest. It would be good if there was. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Also, unless otherwise specified, the direction in which layers are stacked relative to the base material is referred to as "top", or if there is a photocurable layer, the direction from the base material to the photocurable layer is referred to as "top". The opposite direction is called "down". Note that such a setting in the vertical direction is for convenience in this specification, and in an actual embodiment, the "up" direction in this specification may be different from vertically upward.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Further, 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, unless otherwise stated, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In this specification, combinations of preferred aspects are more preferred aspects.

(Pattern formation method)
The pattern forming method of the present invention includes a first region exposure step of selectively exposing a first region, which is a part of a photoresist film made of a photosensitive resin composition, and a step of exposing the photoresist film after the first region exposure step. A second region exposure step of selectively exposing a second region, which is a part of the region, and a development step of developing the photoresist film after the second region exposure step, at least one region included in the first region. The region of the second region and at least a part of the region included in the second region are common regions, and the photosensitive resin composition is a group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. At least one resin selected from the following (hereinafter also referred to as "specific resin") and a photosensitizer are included.

The pattern forming method of the present invention provides an excellent pattern shape.
Although the mechanism by which the above effects are obtained is unknown, it is assumed as follows.

Conventionally, a photoresist film formed from a photosensitive resin composition containing polyimide or polybenzoxazole or a precursor thereof and a photosensitizer is exposed and developed, and then heated if necessary to form a pattern. It has been carried out to form.
As a result of extensive studies, the present inventors found that by performing the first area exposure process and the second area exposure process on the photosensitive film formed from the photosensitive resin composition, the It has been found that the shape of the pattern is suppressed from becoming tapered or inversely tapered.
The amount of radicals, acids, etc. generated from the photosensitizer during one exposure can be reduced by dividing the exposure process into a first area exposure process and a second area exposure process, rather than one exposure process. This is presumed to be because the diffusion of the radicals, acids, etc. in the photoresist film is suppressed as a result.
In the present invention, the angle formed between the surface of the substrate on which the pattern is formed and the side surface of the pattern is called the taper angle, and when the taper angle is much less than 90° (for example, when the taper angle is less than 80°), The pattern shape is called a reverse taper shape, and the pattern shape when the taper angle greatly exceeds 90° (for example, when the taper angle exceeds 100°) is called a tapered shape.
In the present invention, an excellent pattern shape means that the taper angle is close to 90°.
For example, when the photoresist film is a negative-tone photoresist film, which will be described later, the photoresist is easily sensitized, especially in the part of the photoresist film on the exposure light source side in the thickness direction, because the energy of the exposure light is strong. , acids, etc. are likely to be generated. In addition, in the photoresist film on the side opposite to the exposure light source in the thickness direction (for example, the substrate side), the exposure light is attenuated and the energy of the exposure light is weak, making it difficult for the photosensitizer to be exposed. For example, it is thought that radicals, acids, etc. are less likely to be generated. As a result, there is a difference in the degree of curing of the composition between the exposure light source side and the base material side of the photoresist film, and it is thought that the pattern shape tends to become inversely tapered.
In addition, when the photoresist film is a positive photoresist film, which will be described later, especially on the exposure light source side in the thickness direction of the photoresist film, the energy of the exposure light is strong, so the photosensitizer is likely to be sensitized, and for example, acid is likely to be generated. Conceivable. Furthermore, on the side of the photosensitive film opposite to the exposure light source in the thickness direction (for example, the substrate side), the exposure light is attenuated and the energy is weak, making it difficult for the photosensitizer to be sensitized. Conceivable. As a result, there is a difference in the solubility of the composition in the developer between the exposure light source side and the base material side of the photosensitive film, and it is thought that the pattern shape tends to become tapered.
When exposing such a negative-tone photosensitive film or positive-tone photosensitive film in two parts, as a first area exposure process and a second area exposure process, the first area exposure process and Since there is a period of time during which no exposure is performed between the second area exposure step, it is thought that the subsequent diffusion of radicals, acids, etc. is suppressed, and the pattern shape is suppressed from becoming inversely tapered or tapered. .

Here, Patent Document 1 does not describe or suggest a pattern forming method including a first region exposure step and a second region exposure step.
Hereinafter, the pattern forming method of the present invention will be explained in detail.

The pattern forming method of the present invention includes a first region exposure step and a second region exposure step.
Furthermore, in addition to the first region exposure step and the second region exposure step, the pattern forming method of the present invention further includes steps such as a third region exposure step, a fourth region exposure step, and other exposure steps, which will be described later. But that's fine.
In the present invention, steps including exposure of a photosensitive film such as a first area exposure step, a second area exposure step, a third area exposure step, a fourth area exposure step, and other exposure steps are collectively referred to as "exposure step". Also called.

<First area exposure process>
The pattern forming method of the present invention includes a first region exposure step of exposing a part of a photosensitive film made of a photosensitive resin composition.
In the first area exposure step, a photosensitizer, which will be described later, is exposed to light, and the solubility of the photosensitive film in the developer changes.
Specifically, for example, when the photosensitive agent is a photopolymerization initiator described below, polymerization proceeds in the photosensitive film, and the solubility of the photosensitive film in the developer after the first region step decreases.
Further, for example, when the photosensitive agent is a photoacid generator described later and the developer is an alkaline developer described later, acid is generated in the photosensitive film and its solubility in the developer increases.
Further, for example, when the photosensitive agent 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 decreases.
In this way, in the first area exposure step, the sensitization of the photosensitive agent promotes the bonding reaction between the crosslinkable groups contained in the specific resin or crosslinking agent and other groups, thereby making the photosensitive film more resistant to the developer. The solubility may change, and the solubility of the photosensitive film in the developer may change depending on a product generated by chemical change of the photosensitive agent due to exposure to light.

That is, the photoresist film in the present invention may be a positive type photoresist film or a negative type photoresist film.
A positive photoresist film is a photoresist film in which the exposed portion (exposed area) in an exposure process such as a first area exposure process and a second area exposure process is removed by a developer, and a negative photoresist film is A photoresist film whose portions (non-exposed portions) that are not exposed in the exposure step are removed by a developer.
In the present invention, a photosensitive film that utilizes the catalytic action of an acid generated from a photosensitizer upon exposure to light is also referred to as a chemically amplified photosensitive film. The chemically amplified photosensitive film preferably contains a resin having a polarity converting group such as an acid-decomposable group and a photoacid generator.
The thickness of the photosensitive film is not particularly limited, but from the viewpoint of easily obtaining the effects of the present invention, it is preferably 5 μm or more, more preferably 10 μm or more. The upper limit of the thickness is not particularly limited, but is preferably 50 μm or less, more preferably 30 μm or less.

The exposure wavelength in the first area exposure step may be appropriately set as a wavelength to which the photosensitizer described below is sensitive, but is preferably 190 to 580 nm, more preferably 240 to 550 nm, and even more preferably 300 to 450 nm. Particularly preferred is 300 to 420 nm.

In relation to the light source (exposure means), the exposure wavelength is (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line. (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser ( (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic of YAG laser (wavelength 532 nm), and third Examples include harmonics (wavelength: 355 nm). For the photosensitive resin composition of the present invention, exposure to i-line is preferred. This makes it possible to obtain particularly high exposure sensitivity. From the viewpoint of handling and productivity, a broad light source (three wavelengths of g, h, and i-rays) of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
In addition, it is not necessary to use a mask pattern such as a photomask, the degree of freedom in use is improved even if a mask pattern is used, it is easy to remove unnecessary wavelengths, or it is easy to improve the exposure illuminance, and the exposure It is preferable to use a laser light source such as a semiconductor laser for exposure from the viewpoint of shortening the exposure time or improving the life of the exposure light source.

Examples of the method for exposing a part of the photoresist film in the first area exposure step include an exposure method using a known photomask, and an exposure method in which a part of the photoresist film is exposed by laser exposure.

<Second area exposure process>
The pattern forming method of the present invention includes a second region exposure step, which is performed after the first region exposure step, and selectively exposes a second region, which is a part of the photoresist film after the first region exposure step. .
The second area exposure step is similar to the first area exposure step except that at least some areas included in the first area and at least some areas included in the second area are common areas. This can be done by the following method.

The exposure wavelength in the second area exposure step may be appropriately set as a wavelength to which the photosensitizer described below is sensitive, but is preferably 190 to 580 nm, more preferably 240 to 550 nm, and even more preferably 300 to 450 nm. Particularly preferred is 300 to 420 nm.
Further, the exposure wavelength in the second region exposure step may be the same as or different from the exposure wavelength in the first region exposure step, but it is preferably the same.

The exposure means in the second region exposure step is not particularly limited, and the same exposure means as the exposure means in the first region exposure step can be used.
Further, the exposure means in the second region exposure step may be the same as or different from the exposure means in the first region exposure step, but it is preferable that they be the same.

The ratio of the area of the area included in both the first area and the second area to the total area of the first area is preferably 50 to 100%, more preferably 70 to 100%. , more preferably 80 to 100%, particularly preferably 90 to 100%.
Setting the above ratio to 100% is also a preferred embodiment of the pattern forming method of the present invention.

<Third area exposure process, fourth area exposure process>
The pattern forming method of the present invention includes a third region exposure step of selectively exposing a third region that is a part of the photoresist film after the second region exposure step, and the developing step includes a third region exposing the third region. This is a step of developing the photoresist film after the area exposure step, in which at least some areas included in the third area and at least some areas included in either the first area or the second area are Preferably, it is a common area.
Further, the pattern forming method of the present invention includes a third region exposing step of selectively exposing a third region which is a part of the photoresist film after the second region exposing step; a fourth area exposure step of selectively exposing a fourth area that is a part of the subsequent photoresist film; the development step is a step of developing the photoresist film after the fourth area exposure step; At least a part of the area included in the third area is a common area with at least a part of the area included in any of the first area, the second area, and the fourth area, and It is preferable that at least a portion of the region included in the fourth region and at least a portion of the region included in any of the first region, the second region, and the third region are common.

The third region exposure step and the fourth region exposure step can be performed by the same method as the first region exposure step described above.
Further, the exposure wavelengths in the third region exposure step and the fourth region exposure step may be the same as or different from the exposure wavelength in the first region exposure step, respectively, but they must be the same. is preferred.
Further, the exposure means in the third region exposure step and the fourth region exposure step may be the same as or different from the exposure means in the first region exposure step, but they must be the same. is preferred.

The ratio of the area of the area included in both the third area and the area included in at least one of the first area, the second area, and the fourth area to the total area of the third area is: It is preferably 50 to 100%, more preferably 70 to 100%, even more preferably 80 to 100%, and particularly preferably 90 to 100%.
Setting the above ratio to 100% is also a preferred embodiment of the pattern forming method of the present invention.
The ratio of the area of the area included in both the fourth area and the area included in at least one of the first area, the second area, and the third area to the total area of the fourth area is: It is preferably 50 to 100%, more preferably 70 to 100%, even more preferably 80 to 100%, and particularly preferably 90 to 100%.
Setting the above ratio to 100% is also a preferred embodiment of the pattern forming method of the present invention.

<Other exposure processes>
The pattern forming method of the present invention further includes, after the fourth step, other exposure steps other than the above-described first region exposure step, second region exposure step, third region exposure step, and fourth region exposure step. But that's fine.
The pattern forming method of the present invention includes another exposure step of selectively exposing another region that is a part of the photoresist film after the fourth region exposure step, and the developing step includes the other exposure step of the fourth region exposure step. This is a step of developing the photoresist film after the step, and at least a part of the area included in the other area, the first area, the second area, the third area, the fourth area, and another area. It is preferable that the area is a common area with at least a part of the area included in any of the other areas in other exposure steps.
Other exposure steps can be performed in the same manner as the first area exposure step described above.
Further, the other exposure step may be a step of exposing the entire photoresist film (total exposure) instead of a step of exposing a part of the photoresist film made of the photosensitive resin composition.
Furthermore, the exposure wavelengths in the other exposure steps may be the same as or different from the exposure wavelength in the first region exposure step, but are preferably the same.
Further, the exposure means in the other exposure steps may be the same as or different from the exposure means in the first region exposure step, but it is preferable that they be the same.
The pattern forming method of the present invention includes a step of exposing a photosensitive film (the first region exposure step, the second region exposure step, the third region exposure step, the fourth region exposure step, and the other exposure step). ) is preferably included 2 to 10 times in total, more preferably 3 to 8 times, and even more preferably 4 to 7 times.

At least one of the other areas, the first area, the second area, the third area, the fourth area, and other areas in another exposure step with respect to the total area of the other areas. The ratio of the area of the area included in the area and the area included in both is preferably 50 to 100%, more preferably 70 to 100%, even more preferably 80 to 100%, and even more preferably 90 to 100%. Particularly preferred is 100%.
Setting the above ratio to 100% is also a preferred embodiment of the pattern forming method of the present invention.
Further, the ratio of the total area of the area included in the photosensitive film that is exposed at least once to the total area of the area that is exposed at least once is preferably 50 to 100%, and preferably 70 to 100%. It is more preferably 80 to 100%, and particularly preferably 90 to 100%.
Setting the above ratio to 100% is also a preferred embodiment of the pattern forming method of the present invention.

<Interval>
In the pattern forming method of the present invention, from the end of one of the steps of exposing a part of the photoresist film included before the development step to the start of another exposing step. The time and the time not including other exposure steps are preferably 0.1 seconds or more, more preferably 0.5 seconds or more, even more preferably 1 second or more, It is particularly preferable that the time is 5 seconds or more. The upper limit of the above time is not particularly limited, and may be, for example, 24 hours or less.
In the present invention, the time from the end of one exposure process to the start of another exposure process, and which does not include any other exposure process, is also referred to as an "interval".
It is thought that by providing the above-mentioned intervals, the diffusion of radicals, acids, etc. generated by the exposure of the photosensitizer is suppressed, resulting in an excellent pattern shape.
For example, when the photosensitive film contains a crosslinking agent, and its solubility in a developer changes due to crosslinking of components in the photosensitive film (polymerization of a radical crosslinking agent, crosslinking of other crosslinking agents, etc.) It is thought that crosslinking progresses during the above interval, and the field mobility decreases. Therefore, it is thought that the diffusion of radicals, acids, etc. generated when further exposure is performed after the interval is suppressed.
In addition, for example, the photosensitive film is a photosensitive film whose solubility in a developer changes due to structural changes such as deprotection of components in the photosensitive film, such as when the photosensitive film contains a specific resin having a polarity converting group such as an acid-decomposable group. In some cases, the polarity of the field increases during this interval, and the diffusivity of polar molecules is thought to decrease. Therefore, it is thought that the diffusion of acids and the like that would be generated when further exposure is performed after the interval is suppressed.
As an example, when the exposure process is performed a total of four times from a first area exposure process to a fourth area exposure process, the first area exposure process is performed at an interval of 10 seconds, the second area exposure process is performed at an interval of 10 seconds, It is possible to perform the exposure in the following order: a third region exposure step, a 10 second interval, and a fourth region exposure step.
When the step of exposing the photosensitive film is included three or more times, there are a plurality of intervals between the exposures, and the plurality of intervals may be the same or different. Furthermore, when there are multiple intervals, at least one of the multiple intervals is preferably 0.1 seconds or more, more preferably 0.5 seconds or more, and 1 second or more. It is more preferable that the time be 5 seconds or more, and particularly preferably 5 seconds or more. The upper limit of the interval is not particularly limited, and may be, for example, 24 hours or less.
For example, as another example, when the exposure process is performed a total of four times from the first area exposure process to the fourth area exposure process, the first area exposure process is performed at an interval of 5 seconds, the second area exposure process is performed at an interval of 10 It is also possible to perform the exposure in the order of a second interval, a third region exposure step, a 15 second interval, and a fourth region exposure step.
Conversely, when the exposure process is performed four times in total from the first area exposure process to the fourth area exposure process, the first area exposure process is performed at an interval of 15 seconds, the second area exposure process is performed at an interval of 10 seconds. It is also possible to perform the exposure in the following order: , the third region exposure step, the 5 second interval, and the fourth region exposure step.

<Exposure wavelength>
Among the above embodiments, in the pattern forming method of the present invention, the exposure wavelength in the first region exposure step and the second region exposure step is preferably 300 to 450 nm, more preferably 300 to 420 nm. preferable.
Further, when the pattern forming method of the present invention includes the third region exposure step and the fourth region exposure step, the first region exposure step, the second region exposure step, the third region exposure step, Further, the exposure wavelength in the fourth region exposure step is preferably 300 to 450 nm, more preferably 300 to 420 nm.

<Exposure amount>
In the pattern forming method of the present invention, the amount of light that the photoresist film is exposed to in the exposure steps such as the first region exposure step, the second region exposure step, etc. The total amount of exposure from multiple exposures such as a three-area exposure process is preferably 100 to 10,000 mJ/cm 2 , and 200 to 8,000 mJ/cm ² in terms of exposure energy at the wavelength to which the photosensitizer is sensitive. More preferably, it is 000 mJ/cm ² .
Further, the focal position in multiple exposures may be the same or different.
The exposure amount in each step such as the first area exposure step and the second area exposure step is not particularly limited, and as long as the total is within the above exposure amount range, the exposure amount in each step is the same. It may be different or it may be different.
Furthermore, the exposure output in each process such as the first area exposure process and the second area exposure process may be the same or different. For example, it is also preferable to perform exposure with a higher exposure output in the second region exposure step than in the first region exposure step. When exposure is performed a total of four times, from the first region exposure step to the fourth region exposure step, it is also preferable that the later steps are exposed at a higher exposure output.

<Post-exposure heating process>
The pattern forming method of the present invention may include a step of heating after exposure (post-exposure heating step).
The post-exposure heating step may be performed after the exposure step such as the first region exposure step and the second region exposure step and before the development step, or once after the first region exposure step and once after the second region exposure step. It may be performed every time the step of exposing the photoresist film is performed, such as once, or it may be determined whether or not to perform the post-exposure heating step each time the step of exposing the photoresist film is performed. good.
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 temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature.
Further, the temperature increase rate may be changed as appropriate during heating.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used.
Further, during heating, it is also preferable to conduct the heating in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon.

<Film formation process>
The pattern forming method of the present invention may include a film forming step of forming a photosensitive film from a photosensitive resin composition.
The photoresist film in the first area exposure step may be a photoresist film formed in a film forming step, or may be a photoresist film obtained by means such as purchase.
The film forming step is preferably a step in which a photosensitive resin composition is applied to a base material to form a film (layer) to obtain a photosensitive film.

〔Base material〕
The type of base material can be determined as appropriate depending on the application, but includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposited films, There are no particular restrictions on the material, such as a magnetic film, a reflective film, a metal base material such as Ni, Cu, Cr, or Fe, paper, a SOG (Spin On Glass), a TFT (Thin Film Transistor) array base material, or an electrode plate of a plasma display panel (PDP).
In the present invention, semiconductor production base materials are particularly preferred, and silicon base materials, Cu base materials, and mold base materials are more preferred.
Moreover, layers such as an adhesive layer and an oxidized layer may be provided on the surface of these base materials.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
These base materials may be provided with a layer such as an adhesive layer or an oxidized layer made of hexamethyldisilazane (HMDS) or the like on the surface.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
As for the size of the base material, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
Further, as the base material, for example, a plate-shaped base material (substrate) is used.

Further, when forming a photosensitive film on the surface of a resin layer or a metal layer, the resin layer or the metal layer serves as a base material.

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

Specifically, the methods to be applied include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, and an inkjet method. From the viewpoint of uniformity of the thickness of the photosensitive film, spin coating, slit coating, spray coating, and inkjet methods are more preferred, and from the viewpoint of easily obtaining the effects of the present invention, slit coating is preferred. A photoresist film with a desired thickness can be obtained by adjusting the solid content concentration and coating conditions appropriately depending on the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet methods, etc. are preferable, and for rectangular substrates, slit coating and spray coating are preferable. method, inkjet method, etc. are preferred. In the case of spin coating, it can be applied, for example, at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Depending on the viscosity of the photosensitive resin composition and the desired film thickness, it is also preferable to apply the coating at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain uniformity in film thickness, coating can be performed by combining a plurality of rotation speeds.
It is also possible to apply a method in which a coating film that has been previously formed on a temporary support by the above-mentioned application method is transferred onto a base material.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention.
Further, a step of removing excess film may be performed at the end of the base material. Examples of such processes include edge bead rinsing (EBR), air knife, back rinsing, and the like. A pre-wet process may be employed in which various solvents are applied to the base material before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.

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

<Developing process>
The pattern forming method of the present invention includes a developing step of developing the exposed photosensitive film with a developer to obtain a pattern.
By performing development, one of the exposed area and the non-exposed area is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection from a nozzle, spraying, and immersion of the substrate in a developer, with ejection from a nozzle being preferably used. The development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a nearly stationary state on the base material, a process in which the developer is vibrated with ultrasonic waves, etc., and a process in which these are combined. Adoptable.

Development is performed using a developer. For negative development, use a developer that removes the unexposed area (unexposed area), and for positive development, use a developer that removes the exposed area (exposed area). , can be used without any particular restrictions.
The development in the development step according to the present invention is preferably carried out using an organic solvent as a developer, and is carried out using a developer containing 50% by mass or more of an organic solvent based on the total mass of the developer. It is more preferable.
Further, the developer may contain a known surfactant.
In the present invention, the case where an alkaline developer is used as a developer is called alkaline development, and the case where a developer containing an organic solvent in an amount of 50% by mass or more based on the total weight of the developer is called solvent development.

In alkaline development, the developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developer, more preferably 5% by mass or less, and 1% by mass or less. A developer solution containing no organic solvent is more preferred, and a developer solution containing no organic solvent is particularly preferred.
The developing solution for alkaline development is preferably an aqueous solution having a pH of 10 to 15.
Examples of alkaline compounds contained in the developer in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include acid potassium, ammonia, or amines. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide. Among these, metal-free alkali compounds are preferred, and ammonium compounds are more preferred.
When using TMAH as the alkali compound, for example, the content of TMAH is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass based on the total mass of the developer. Mass % is more preferred.
The number of alkali compounds may be one, or two or more. When there are two or more types of alkali compounds, it is preferable that the total is within the above range.

In solvent development, it is more preferable that the developer 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.

Examples of 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, and γ-butyrolactone. , ε-caprolactone, δ-valerolactone, alkyloxy acetate (e.g. methyl alkyloxy acetate, ethyl alkyloxy acetate, butyl alkyloxy acetate (e.g. methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-methoxypropionate, 3-methoxypropionate, etc.) ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., 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. , Ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons such as toluene, xylene, anisole, limonene, etc. Dimethyl sulfoxide is preferably mentioned as the sulfoxide.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used.
The developer may further contain other components. Examples of other components include known surfactants and known antifoaming agents.
[Developer supply method]
There are no particular restrictions on the method of supplying the developer as long as the desired pattern can be formed, such as immersing the substrate in the developer, paddle development in which the developer is supplied onto the substrate using a nozzle, or continuous development. One example is a method of supplying. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
From the viewpoint of permeability of the developer, removability of non-image areas, and production efficiency, it is preferable to supply the developer using a straight nozzle or continuously using a spray nozzle. From the viewpoint of permeability, a method of supplying with a spray nozzle is more preferable.
In addition, after continuously supplying the developer using a straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied again using the straight nozzle, the base material is spun, and the developer is applied to the base material. A process of removing from above may be adopted, or this process may be repeated multiple times.
In addition, the developer supply method in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is kept in an almost stationary state on the base material. A process of vibrating with a sound wave or the like, a process of combining these, etc. can be adopted.

The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but it can usually be carried out at 10 to 45°C, more preferably at 20 to 40°C.

In the development process, rinsing may be further performed after the treatment using the developer. Alternatively, a method may be adopted in which a rinsing liquid is supplied before the developer in contact with the pattern is completely dried.
In the case of solvent development, rinsing is preferably performed with an organic solvent different from the developer.
In the case of alkaline development, rinsing is preferably performed using pure water.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, even more preferably 5 seconds to 1 minute.
The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
When the rinsing liquid contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, methoxyacetic acid) ethyl, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), 3-alkyloxypropionate alkyl esters (e.g. methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkyloxypropionate esters (for example, methyl 2-alkyloxypropionate, - Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate) methyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate) methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, etc.; examples of sulfoxides include dimethyl sulfoxide; examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, Preferred examples include methylisobutylcarbinol, triethylene glycol, etc., and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
When the rinsing liquid contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are particularly preferred. More preferred.
When the rinsing liquid contains an organic solvent, the rinsing liquid preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and 90% by mass or more of an organic solvent. is even more preferable. Moreover, 100% by mass of the rinsing liquid may be an organic solvent.
The rinse solution may further contain other components.
Examples of other components include known surfactants and known antifoaming agents.
[How to supply rinsing liquid]
There are no particular restrictions on the method of supplying the rinse liquid as long as the desired pattern can be formed, and the methods include immersing the substrate in the rinse liquid, developing with a puddle on the substrate, supplying the rinse liquid onto the base material with a shower, and the method of supplying the rinse liquid to the base material. The above method includes a method of continuously supplying the rinsing liquid using means such as a straight nozzle.
From the viewpoint of permeability of the rinsing liquid, removability of non-image areas, and manufacturing efficiency, it is preferable to supply the rinsing liquid through a shower nozzle, straight nozzle, spray nozzle, etc., and a method in which the rinsing liquid is continuously supplied using a spray nozzle. is more preferable. From the viewpoint of permeability of the rinse liquid into the image area, a method of supplying the rinse liquid with a spray nozzle is more preferable. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
That is, the rinsing step is preferably a step in which the rinsing liquid is supplied to the exposed film through a straight nozzle or continuously, and more preferably a step in which the rinsing liquid is supplied through a spray nozzle.
In addition, the rinsing liquid supply method in the rinsing process includes a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept in a substantially stationary state on the substrate, and a process in which the rinsing liquid is A process of vibrating with a sound wave or the like, a process of combining these, etc. can be adopted.

<Heating process>
The manufacturing method of the present invention preferably includes a step of heating the developed film (heating step).
In the heating step, for example, when the photosensitive film contains a precursor such as a polyimide precursor or a polybenzoxazole precursor, or when the photosensitive film contains a crosslinkable component such as a crosslinking agent, the cured pattern ( This makes it possible to obtain a cured film (also referred to as a "cured film").
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, crosslinking of unreacted crosslinking agent can proceed. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 140°C or higher, and even more preferably 150°C or higher. The temperature is more preferably 160°C or higher, even more preferably 170°C or higher. The upper limit is preferably 500°C or less, more preferably 450°C or less, even more preferably 350°C or less, even more preferably 250°C or less, and even more preferably 220°C or less. Even more preferred.

Heating is preferably carried out at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the heating rate to 12°C/min or less, the pattern can be improved. The residual stress can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 8 degrees Celsius/second, more preferably 2 to 7 degrees C/second, and 3 to 6 degrees Celsius. C/sec is more preferred.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when drying a photosensitive resin composition after applying it on a substrate, the temperature of the film (layer) after drying is, for example, higher than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from a low temperature of 30 to 200°C.

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

Particularly when forming a multilayer laminate, heating is preferably performed at a temperature of 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between layers of the pattern. Although the reason for this is not clear, it is thought that at this temperature, the ethynyl groups of the specific resin between the layers undergo a crosslinking reaction with each other.

Heating may be performed in stages. As an example, the temperature is raised from 25°C to 180°C at a rate of 3°C/min, held at 180°C for 60 minutes, and the temperature is raised from 180°C to 200°C at a rate of 2°C/min, and held at 200°C for 120 minutes. You may perform a pretreatment process such as . 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 perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out 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, pretreatment step 1 may be performed at a temperature of 100 to 150°C, followed by pretreatment step 2 at a temperature of 150 to 200°C.

Furthermore, 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 performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and includes, for example, a hot plate, an infrared oven, an electric oven, a hot air oven, and the like.

<Metal layer formation process>
The pattern forming method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the pattern after an exposure step such as a first region exposure step and a second region exposure step.

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

The method for forming the metal layer is not particularly limited, and any existing method can be applied. For example, methods described in JP-A No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, JP-A No. 2004-214501, and JP-A No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these methods can be used. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned.

The thickness of the metal layer is, for example, 0.01 to 100 μm at the thickest portion, preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

<Application>
Fields to which the pattern obtained by the pattern forming method of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other methods include forming a pattern by etching 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 purposes as described above. Regarding these uses, for example, Science & Technology Co., Ltd., "Advanced Functionality and Applied Technology of Polyimide", April 2008, Masaaki Kakimoto/Supervised, CMC Technical Library, "Basics and Development of Polyimide Materials", November 2011. You can refer to "Latest Polyimide Basics and Applications" published by Japan Polyimide and Aromatic Polymer Research Society/editor, NTS, August 2010, etc.

The patterns obtained by the patterning method of the invention can also be used in the production of plates such as offset plates or screen plates, in the etching of molded parts, in the production of protective lacquers and dielectric layers in electronics, in particular in microelectronics, etc. It can also be used.

(Method for manufacturing laminate)
It is preferable that the method for manufacturing a laminate of the present invention 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 with 3 to 7 layers laminated.
The pattern included in the laminate of the present invention may be the above-mentioned cured film.
At least one of the two or more layers of patterns included in the laminate is a pattern obtained by the pattern forming method of the present invention, and from the viewpoint of improving the pattern shape, all the patterns included in the laminate are Preferably, the pattern is obtained by the pattern forming method of the present invention.
Preferably, 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.
A preferred example of the laminate is a laminate that includes at least a layered structure in which three layers, a first pattern, a metal layer, and a second pattern are laminated in this order.
It is preferable that the first pattern and the second pattern are both 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. Alternatively, they may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Lamination process>
It is preferable that the method for manufacturing a laminate of the present invention includes a lamination step.
The lamination process means that the surface of the pattern or metal layer is again subjected to (a) film formation process (layer formation process), (b) first area exposure process, (c) second area exposure process, and (d) development process. , in this order.
However, an embodiment may be adopted in which only the film forming step (a) is repeated, and then the steps after the first region exposure step (b) are performed. Further, after the second region exposure step (c) described above, one or more steps of exposing, such as a third region exposure step and a fourth region exposure step, may be included.
Moreover, the above-mentioned heating step may be included after the above-mentioned (d) developing step.
Further, after the (d) development step, the above-mentioned metal layer forming step may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.

When a lamination step is further performed after the lamination step, a surface activation treatment step may be performed after the exposure step, the development step, the heating step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.

The above lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a structure including resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, in which the number of resin layers is 2 to 20 layers, is preferably 3 to 7 layers. , a structure having 3 or more layers and 5 or less layers is more preferable.
Further, each layer in the lamination process may be the same layer in composition, shape, thickness, etc., or may be a different layer.
<Surface activation treatment process>
The method for producing a cured film of the present invention may include a surface activation treatment step of surface activation treatment of at least a portion of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but it is also possible to perform the metal layer formation step after performing the surface activation treatment step on the photosensitive resin composition layer after the exposure and development step. good.
The surface activation treatment may be performed on at least a portion of the metal layer, or may be performed on at least a portion of the photosensitive resin composition layer after exposure, or the surface activation treatment may be performed on at least a portion of the metal layer and the photosensitive resin composition layer after exposure. Both composition layers may each be applied at least in part. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on part or all of the region of the metal layer on which the photosensitive resin composition layer is to be formed. . By performing surface activation treatment on the surface of the metal layer in this way, it is possible to improve the adhesion with the resin layer provided on the surface.
Moreover, it is preferable that the surface activation treatment is also performed on part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing surface activation treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion with the metal layer or resin layer provided on the surface that has been surface activated.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF ₄ /O ₂ , etching treatment with NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment with ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then removing amino groups and thiol groups. The surface treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound, and mechanical surface roughening treatment using a brush, and plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

In the present invention, it is particularly preferable that after the metal layer is provided, a pattern of the photosensitive resin composition is further formed so as to cover the metal layer. Specifically, the order of (a) film formation step (layer formation step), (b) first region exposure step, (c) second region exposure step, (d) development step, and (e) metal layer formation step. An example of this is a repeating mode. By alternately performing the steps (a) to (d) for forming a pattern and the metal layer forming step, patterns and metal layers can be alternately laminated.

(Method for manufacturing electronic devices)
The present invention also discloses a method for manufacturing a semiconductor device including the pattern forming method of the present invention or the method for manufacturing a laminate of the present invention. For specific examples of semiconductor devices using the photosensitive resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, please refer to paragraphs 0213 to 0218 of JP-A No. 2016-027357 and the description in FIG. and the contents thereof are incorporated herein.
Hereinafter, details of the photosensitive resin composition used in the pattern forming method of the present invention, the method of manufacturing a laminate of the present invention, or the method of manufacturing a semiconductor device of the present invention will be described.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention is a photosensitive resin composition used in the pattern forming method of the present invention, the method of manufacturing a laminate of the present invention, or the method of manufacturing a semiconductor device of the present invention.
The photosensitive resin composition of the present invention contains at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, and a photosensitizer.
Hereinafter, details of each component contained in the photosensitive resin composition of the present invention will be explained.

<Specific resin>
The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.
The photosensitive resin composition of the present invention preferably contains polyimide or a polyimide precursor, and more preferably contains a polyimide precursor, as the specific resin.
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 radical photopolymerization initiator described below as a photosensitizer, and contains a radical photopolymerization initiator described below as a photosensitizer, and It is more preferable to include a radical crosslinking agent as described below, and it is even more preferable to include a photoradical polymerization initiator described below as a photosensitizer, a radical crosslinking agent described below, and a sensitizer described below. For example, a negative photosensitive layer is formed from such a photosensitive resin composition.
Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator described below as a photosensitizer. From such a photosensitive resin composition, for example, a chemically amplified positive-type photosensitive layer or a negative-type photosensitive layer is formed.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly limited in its type, but 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, and preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. A particularly preferred embodiment of the present invention is a group represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , -SO ₂ -, NHCO-, or a combination of two or more of the above. These preferred ranges are as described above.

Preferably R ¹¹¹ is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. 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. A diamine containing a group containing an aromatic group having 6 to 20 carbon atoms is preferable, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include the following.

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO _2- , NHCO-, or a combination thereof, and is preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -C( A group selected from =O)-, -S-, or -SO ₂ - is more preferable, and -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - is more preferable.
In the formula, * represents a bonding site with another structure.

Specifically, the diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; 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 Diphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 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-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'-diamino Diphenylmethane, 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)octafluorobutane, 1, 5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis [4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis( 4-Amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) ) 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-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5 At least one diamine selected from ',6,6'-hexafluorotridine and 4,4'-diaminoquaterphenyl is mentioned.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.

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

From the viewpoint of flexibility of the resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , -SO ₂ -, NHCO-, or 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.

Moreover, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferable.
Formula (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 It is a methyl group.
The monovalent organic groups R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include fluorinated alkyl groups.
In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound giving 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'-diaminoctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.
Further, the following diamines can also be suitably used.

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 formula (6) is more preferable. Formula (5)
In formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , NHCO-, and a combination thereof, preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom, -O-, -CO A group selected from -, -S- and SO ₂ - is more preferable, and -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO More preferably, it is a divalent group selected from the group consisting of -, -S- and SO ₂ -.

Formula (6)

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. One type of tetracarboxylic dianhydride may be used, or two or more types may be used.
It is preferable that the tetracarboxylic dianhydride is 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 the same as R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfidetetracarboxylic 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 Examples include alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes a residue of a bisaminophenol derivative.

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, and more preferably both contain a polymerizable group. preferable. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group. Examples include groups. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

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.
Suitable examples of R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group , -CH ₂ CH(OH)CH ₂ -, and polyalkyleneoxy groups, and ethylene group, propylene group, trimethylene group, -CH ₂ CH(OH)CH ₂ -, and polyalkyleneoxy groups are more preferable, and organic membrane From the viewpoint of making it easier to satisfy formula (2), a polyalkyleneoxy group is more preferable.
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 an arrangement having blocks. Alternatively, an arrangement having an alternating pattern or the like may be used.
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 preferable, 2 to 5 is even more preferable, 2 to 4 is even more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Further, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
Further, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
From the viewpoint of solvent solubility and solvent resistance, polyalkyleneoxy groups include polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or multiple ethyleneoxy groups and multiple propyleneoxy groups. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is even more preferable. In the above-mentioned group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in an alternating pattern. Preferred embodiments of the repeating number of ethyleneoxy groups, etc. in these groups are as described above.

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

From the viewpoint of solubility in 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, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of straight-chain or branched alkyl groups include 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 ) ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group, and pinenyl group. can be mentioned. Among these, a cyclohexyl group is most preferred from the viewpoint of achieving both high sensitivity and high sensitivity. Further, as the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described below is preferable.
Specific examples of the aromatic group 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, They are a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiine ring, a phenothiazine ring, or a phenazine ring. Most preferred is a benzene ring.

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

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

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

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

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one type of polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (2-A). With such a structure, it is possible to further widen 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, and R ¹¹³ and R ¹¹⁴ each independently, It represents a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and preferably both are polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and their preferred ranges are also the same. .
R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred ranges are 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. Further, it may contain a structural isomer of the repeating unit represented by formula (2). Moreover, it goes without saying that 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, a polyimide precursor in which 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) is used. Illustrated.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. Further, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly determined, but for example, it is preferably 4.5 or less, more preferably 4.0 or less, even more 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 this specification, the molecular weight dispersity is a value calculated from weight average molecular weight/number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23°C in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and from the viewpoint of pattern formation, 0.5 g or more. The polyimide is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. The upper limit of the amount dissolved is not particularly limited, but is preferably 100 g or less.
Further, from the viewpoint of film strength and insulation properties of the organic film obtained, the polyimide is preferably a polyimide having a plurality of imide structures in its main chain.
As used herein, the term "main chain" refers to the relatively longest bonding chain in the molecules of the polymer compound constituting the resin, and the term "side chain" refers to other bonding chains.

-Fluorine atom-
From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has a fluorine atom.
The fluorine atom is preferably included in, for example, R ¹³² in the repeating unit represented by formula (4) described later or R 131 in the repeating unit represented by formula (4) described later, and is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later. It is more preferable that R ¹³² in the repeating unit represented by formula (4) or R ¹³¹ in the repeating unit represented by formula (4) described below be included as a fluorinated alkyl group.
The amount of fluorine atoms based on 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, it is preferable that the polyimide contains silicon atoms.
The silicon atom is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later, and is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later. ) More preferably, it is included as a siloxane structure.
The silicon atom or the organically modified (poly)siloxane structure may be included in the side chain of the polyimide, but is preferably included in the main chain of the polyimide.
The amount of silicon atoms based on the total mass of the 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 ethylenically unsaturated bonds.
Polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable to have it in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably included in R ¹³² in the repeating unit represented by formula (4) described below or R 131 in the repeating unit represented by formula (4) described later, and is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described below. It is more preferable that R ¹³² in the repeating unit represented by (4) or R ¹³¹ in the repeating unit represented by formula (4) described below be included as a group having an ethylenically unsaturated bond.
Among these, an ethylenically unsaturated bond is preferably included in R 131 in the repeating unit represented by the formula (4) described later, and ethylene is included in R ¹³¹ in the repeating unit represented ^by the formula (4) described later. More preferably, it is included as a group having a sexually unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinyl phenyl group, a (meth)acrylamide group, and a (meth)acrylamide group. 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, particularly preferably 2 or 3; the number of repeats is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a combination of two or more thereof.

Among these, R ²¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by 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 combining two or more of these; 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) is bonded.
In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the group having 2 to 12 carbon atoms in R ²¹ described above. The preferred embodiments are the same as 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) includes, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained by, for example, 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 (for example, glycidyl methacrylate). can get.

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

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

-Crosslinkable groups other than ethylenically unsaturated bonds-
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 R ¹³¹ in the repeating unit represented by formula (4) described below, for example.
The amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

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

-Acid value-
When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more. It is more preferable that
Further, 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 below), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, and 3 to 30 mgKOH/g. /g is more preferable, and 5 to 20 mgKOH/g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
Further, as the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable.
pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In this specification, pKa is a value calculated by ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, you may refer to the values published in "Revised 5th Edition Chemistry Handbook Basic Edition" edited by the Chemical Society of Japan.
Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.

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

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 having a polymerizable group, the polymerizable group may be located at at least one of R ¹³¹ and R ¹³² , or may be located at the terminal end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in
Formula (4-1)
In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as in formula (4).
Formula (4-2)
At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include those similar to R ¹¹¹ in formula (2), and the preferred ranges are also the same.
Furthermore, examples of R ¹³¹ include diamine residues remaining after removal of the amino group of diamine. Examples of diamines include aliphatic, cycloaliphatic, and aromatic diamines. A specific example is 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 in order to more effectively suppress the occurrence of warpage during firing. More preferred is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferred is a diamine residue containing no aromatic ring.

Examples of 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. 1-(2-(2-(2-aminopropoxy)ethoxy) Examples include, but are not limited to, 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 include those similar to R ¹¹⁵ in formula (2), and the preferred ranges are 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.

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

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples. As R ¹³² , the above (DAA-1) to (DAA-5) are mentioned as more preferable examples.

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

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

Additionally, in order to improve the storage stability of the composition, the main chain ends of polyimide may be capped with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, mono-acid chloride compounds, and mono-active ester compounds. preferable. Among these, it is more preferable to use monoamines, and preferable 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- Examples include aminothiophenol and 4-aminothiophenol. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal capping agents.

-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of film strength, insulation properties, etc. of the organic film obtained. 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 above imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of polyimide is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure, is determined. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 around 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1/peak intensity P2) x 100

The polyimide may include repeating structural units of the above formula (4) that all contain one type of R ¹³¹ or R ¹³² , or the above formula (4) that contains two or more different types of R ¹³¹ or R ¹³² . may contain repeating units. Moreover, the polyimide may also contain other types of repeating structural units in addition to the repeating units of the above formula (4).

Polyimide can be produced, for example, by reacting tetracarboxylic dianhydride with a diamine compound (partly substituted with a monoamine terminal capping agent) at low temperatures, or by reacting tetracarboxylic dianhydride (partly substituted with an acid terminal capping agent) at low temperature. A method of reacting a diamine compound with a terminal capping agent that is an anhydride or a monoacid chloride compound or a monoactive ester compound, a diester is obtained by reacting a tetracarboxylic dianhydride and an alcohol, and then a diamine (partially substituted with a monoamine) is reacted with a diamine compound. A diester is obtained by reacting tetracarboxylic dianhydride with an alcohol in the presence of a condensing agent, and then the remaining dicarboxylic acid is converted into an acid chloride, and a diamine (a portion of which is replaced with a monoamine) is reacted with a condensing agent. A polyimide precursor is obtained using a method such as reacting with a terminal capping agent (substituted with an end-capping agent), and this is completely imidized using a known imidization reaction method, or a polyimide precursor is completely imidized using a known imidization reaction method. Synthesis can be carried out by stopping the chemical reaction and partially introducing an imide structure, or by blending a completely imidized polymer with its polyimide precursor to partially introduce an imide structure. Can be done.
Examples of commercially available polyimides include Durimide (registered trademark) 284 (manufactured by Fuji Film Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Corporation).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when containing two or more types of polyimides, it is preferable that the weight average molecular weight of at least one type of polyimide is within the above range.

[Polybenzoxazole precursor]
Although the structure of the polybenzoxazole precursor used in the present invention is not particularly limited, 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. represent.

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 of them is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. 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, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. The straight chain or branched (preferably straight chain) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, even more preferably 3 to 20 carbon atoms, and 4 to 30 carbon atoms. It is more preferably 15, and particularly preferably 5-10. Preferably, the straight chain aliphatic group is an alkylene group.
Examples of 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, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic 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, tria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

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

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

In the formula, A is -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - represents a divalent group selected from the group consisting of, and * each independently represents a bonding site with 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, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-Diamino-3,3'-dihydroxybiphenyl,3,3'-diamino-4,4'-dihydroxydiphenylsulfone,4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino- 4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

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

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # each represent other structures represents the binding site of Further, it is also preferable that R ¹²² has a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the four * and # are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and The other two are preferably bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded. , and two #s are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded. and two #s are preferably bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. More preferably, it is a bonding site with an atom, and the 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). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is 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.

(In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bis-aminophenol derivative represented by formula (A-s) above.)

In the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxyl group, that is, at _R3 , is thought to bring the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer; It is particularly preferred in that the effect of achieving a high cyclization rate is further enhanced.

In addition, in the above formula (A-s), R ₂ is an alkyl group and R ₃ is an alkyl group, which results in high transparency to i-rays and a high cyclization rate when cured at low temperature. It is preferable because the effect can be maintained.

Further, in the above formula (A-s), it is more preferable that R ₁ is alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene for R ₁ include -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ )-, -C (CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ )(CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -CH(CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH(CH ₃ ) ₂ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH ₂ CH(CH ₃ ) ₂ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, etc., among which -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - is a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperatures. It is more preferable in that it can be obtained.

For the method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, refer to paragraph numbers 0085 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP-A No. 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 paragraph numbers 0070 to 0080 of JP-A No. 2013-256506, the contents of which are herein incorporated by reference. be incorporated into. Of course, it goes without saying that it is not limited to these.

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

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

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

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further Preferably it is 22,000 to 28,000. Further, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and 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. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.

[Polybenzoxazole]
The 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) More preferably, it is a compound having a polymerizable group. The above polymerizable group is preferably a radically polymerizable group. Further, the compound represented by the following formula (X) may be a compound having a polarity converting 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.
When having a polar converting group such as a polymerizable group or an acid-decomposable group, the polar converting group such as a polymerizable group or an acid-decomposable group may be located at at least one of R ¹³³ and R ¹³⁴ , or the following It may be located 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 converting group such as a polymerizable group or an acid-decomposable group, and when it is not a polar converting group such as a polymerizable group or an acid-decomposable group, It is an organic group, and the other groups have the same meanings as in formula (X).
Formula (X-2)
In formula (X-2), R ¹³⁷ is a polarity converting group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups have the same meanings as in formula (X).

The polarity converting group such as a polymerizable group or an acid-decomposable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor.

R ¹³³ represents a divalent organic group. Divalent organic groups include aliphatic or aromatic groups. A specific example includes R ¹²¹ in formula (3) of the polybenzoxazole precursor. Moreover, the preferable example is the same as ^R121 .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in formula (3) of the polybenzoxazole precursor. Moreover, the preferable example is the same as ^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, the following structure is formed.

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

The polybenzoxazole may contain repeating structural units of the above formula (X) all containing one type of R ¹³¹ or R ¹³² , or repeating structural units of 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 can be 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 dicarboxylic acid, to obtain a polybenzoxazole precursor. , can be obtained by oxazolizing this using a known oxazolization reaction method.
In the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative which has been reacted with 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 the 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 bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when containing two or more types of polybenzoxazole, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is within the above range.

[Method for producing polyimide precursor, etc.]
Polyimide precursors and the like are obtained by reacting dicarboxylic acids or dicarboxylic acid derivatives with diamines. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.
In the method for producing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one or two or more.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
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 applying a catalyst), or by direct production. , polyimide may be synthesized.

-Terminal sealing agent-
When manufacturing polyimide precursors, etc., in order to further improve storage stability, the ends of polyimide precursors, etc. are closed with an end-capping agent such as an acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Preferably, it is sealed. As the terminal capping agent, it is more preferable to use a monoamine, and preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-ethynylaniline. 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 types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal capping agents.

-Solid precipitation-
The production of the polyimide precursor and the like may include a step of precipitating a solid. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor etc. in the reaction solution in water and dissolving it in a solvent such as tetrahydrofuran in which the polyimide precursor etc. can be dissolved.
Thereafter, the polyimide precursor and the like can be dried to obtain a powdery polyimide precursor and the like.

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

<Other resins>
The composition of the present invention may contain the above-described specific resin and another resin (hereinafter also simply referred to as "other resin") different from the specific resin.
Other resins include polyamide-imide, polyamide-imide precursors, phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, acrylic resins, and the like.
For example, by further adding an acrylic resin, a composition with excellent coating properties and an organic film with excellent solvent resistance can be obtained.
For example, by adding to the composition an acrylic resin with a high polymerizable group value and a weight average molecular weight of 20,000 or less, instead of or in addition to the polymerizable compound described below, It is possible to improve the coating properties of objects, the solvent resistance of organic films, etc.

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 based on the total solid content of the composition. It is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. .
Further, 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, and 70% by mass based on the total solid content of the composition. It is more preferably at most 60% by mass, even more preferably at most 50% by mass.
Further, as a preferable embodiment of the composition of the present invention, the content of other resins can be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less based on the total solid content of the composition. The content is more preferably 5% by mass or less, even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types of other resins. When two or more types are included, it is preferable that the total amount falls within the above range.

<Photosensitizer>
The composition of the present invention includes a photosensitizer.
As the photosensitizer, a photopolymerization initiator is preferred.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.
The photopolymerization initiator is preferably a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible range is preferred. Alternatively, the activator may be an activator that generates active radicals by having some effect with the photoexcited sensitizer.

In an organic film, from the viewpoint of easily satisfying the above-mentioned formula (2), the composition of the present invention preferably contains a metal element-containing compound described below as a photoradical polymerization initiator. That is, in the present invention, among the metal element-containing compounds described below, those having the ability to initiate radical polymerization can be used as the photoradical polymerization initiator.
Here, having the ability to initiate radical polymerization means being able to generate free radicals that can initiate radical polymerization. For example, for a composition containing a radically polymerizable monomer, a binder polymer, and a metal element-containing compound, a wavelength range in which the metal element-containing compound absorbs light and a wavelength range in which the radically polymerizable monomer does not absorb light is determined. The presence or absence of polymerization initiation ability can be confirmed by confirming whether the radically polymerizable monomer disappears when irradiated with light. To confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radically polymerizable monomer or binder polymer, but for example, confirmation by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography) good.

When the composition of the present invention contains a metal element-containing compound having the ability to initiate radical polymerization, it is also preferable that the composition of the present invention does not substantially contain any radical polymerization initiator other than the metal element-containing compound. "Substantially free of radical polymerization initiators other than the metal element-containing compound" means that the content of the radical polymerization initiator other than the metal element-containing compound in the composition of the present invention is substantially free of the radical polymerization initiator other than the metal element-containing compound. 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass, based on the total mass of.
Furthermore, when the composition of the present invention contains a metal element-containing compound having the ability to initiate radical polymerization, the composition of the present invention may also contain the metal element-containing compound and another photoradical polymerization initiator. preferable.
When the composition of the present invention contains a metal element-containing compound and another photoradical polymerization initiator, the content of the metal element-containing compound relative to the total content of the metal element-containing compound and the other photoradical polymerization initiator. The amount is preferably 20 to 80% by weight, more preferably 30 to 70% by weight.
Further, as the other photoradical polymerization initiator, the oxime compounds described below are preferable.

The photoradical polymerization initiator must contain at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ within the range of about 300 to 800 nm (preferably 330 to 500 nm). is preferred. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, 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. Can be mentioned. For these details, the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated herein.

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

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone initiator described in JP-A-10-291969 and the acylphosphine oxide initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127, IRGACURE 727 (trade name: all manufactured by BASF) can be used.

As the aminoacetophenone initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone initiator, a compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a light source having a wavelength of 365 nm or 405 nm can also be used.

Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Furthermore, commercially available products IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF). The metallocene compound includes a metal element-containing compound described below and having the ability to initiate radical polymerization.

More preferred examples of the photoradical polymerization initiator include oxime compounds. By using an oxime compound, it becomes possible to improve exposure latitude more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

As specific examples of the oxime compound, compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166 can be used.

Preferred oxime compounds include, for example, compounds with the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-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 composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a >C=N-O-C(=O)- linking group in the molecule.

光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物、特許０６６３６０８１号に記載の化合物が挙げられる。
光重合開始剤としては、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, the light described in JP-A No. 2012-014052). Radical polymerization initiator 2) is also suitably used. Additionally, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), ADEKA ARCLES NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Moreover, oxime compounds having the following structures can also be used.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A No. 2014-137466 and compounds described in Japanese Patent No. 06636081.
As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

It is also possible to use an oxime compound containing a fluorine atom. Specific examples of such oxime compounds include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and JP-A No. 2013-2013. Examples include the compound (C-3) described in paragraph 0101 of Publication No. 164471.

The most preferred oxime compounds include oxime compounds having specific substituents as shown in JP-A No. 2007-269779, and oxime compounds having a thioaryl group as shown in JP-A No. 2009-191061.

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryl compounds. 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. Compounds such as

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

In addition, photoradical polymerization initiators include 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, alkylanthraquinone, etc. It is also possible to use 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. Moreover, a compound represented by the following formula (I) can also be used.

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

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

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

When a photopolymerization 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 0.5 to 15% by weight, even more preferably 1.0 to 10% by weight. The photopolymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range.

[Photoacid generator]
Moreover, it is also preferable that the composition of the present invention contains a photoacid generator as a photosensitizer.
By containing a photoacid generator, for example, an acid is generated in the exposed area of the composition layer, increasing the solubility of the exposed area in a developer (e.g., aqueous alkaline solution), and making the exposed area more susceptible to the developer. A positive pattern that is removed can be obtained.
In addition, when the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described below, for example, the crosslinking reaction of the polymerizable compound is promoted by the acid generated in the exposed area, It is also possible to adopt a mode in which exposed areas are more difficult to be removed by a developer than non-exposed areas. According to this aspect, a negative pattern can be obtained.

Photoacid generators are not particularly limited as long as they generate acid upon exposure to light, but include quinonediazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, imidosulfonates, and oximes. Examples include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.

Quinonediazide compounds include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, those in which the sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide bond, and those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through an ester bond and a sulfonamide bond. Examples include those bound by at least one of the following. In the present invention, for example, it is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinonediazide, either a 5-naphthoquinonediazide sulfonyl group or a 4-naphthoquinonediazide sulfonyl group is preferably used. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 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-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinonediazide sulfonyl group or a 5-naphthoquinonediazide sulfonyl group may be contained in the same molecule, or a 4-naphthoquinonediazide sulfonyl ester compound and a 5-naphthoquinonediazide sulfonyl ester compound may be contained in the same molecule. May be contained.

The above naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, resolution, sensitivity, and film retention rate are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. It will be done.

Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A No. 2008-013646.
In addition, commercially available products may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all Fujifilm Wa (manufactured by Hikari Junyaku Co., Ltd.), etc.

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 composition of the present invention. , more preferably 2 to 15% by mass. The photoacid generator may contain only one type, or may contain two or more types. When containing two or more types of photoacid generators, it is preferable that the total is 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. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , ε-caprolactone, δ-valerolactone, alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-methoxypropionate, 3-methoxypropionate), ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Preferred examples include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like. .

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

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like.

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

Suitable examples of sulfoxides include dimethyl sulfoxide.

Amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N- Preferred examples include dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of 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- Consisting of one or more solvents 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 Mixed solvents are preferred. Particularly preferred is the combination of dimethyl sulfoxide and γ-butyrolactone. Also preferred are combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone.

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

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

<Thermal polymerization initiator>
The composition of the invention may also contain a thermal polymerization initiator, in particular a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals using thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding a thermal radical polymerization initiator, it is possible to advance the polymerization reaction of the resin and the polymerizable compound in the heating step described below, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 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. The thermal polymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of thermal polymerization initiators, it is preferable that the total amount is within the above range.

<Thermal acid generator>
Compositions of the invention may also include a thermal acid generator.
The thermal acid generator generates acid by heating and promotes the crosslinking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound. It has the effect of

The thermal decomposition starting 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: approximately 70 to 140°C) after applying the composition to the substrate, and during final heating (curing: approximately 100 to 400°C) after patterning by subsequent exposure and development. It is preferable to select a thermal acid generator that generates an acid because it can suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the peak temperature of the lowest exothermic peak when the thermal acid generator is heated to 500° C. at 5° C./min in a pressure-resistant capsule.
Examples of equipment used to measure the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, such as arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or trifluoromethane. Haloalkylsulfonic acids such as sulfonic acids are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A No. 2013-072935.

Among these, those that generate alkyl sulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferable, from the viewpoint that there is little residual in the organic film and it is difficult to deteriorate the physical properties of the organic film, and methanesulfonic acid is preferable. (4-hydroxyphenyl)dimethylsulfonium, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl) carbonyl)oxy)phenyl)methylsulfonium, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (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) Propane nitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as the thermal acid generator.

Further, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferable as a thermal acid generator.

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, based on 100 parts by mass of the resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, the content 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>
Preferably, the composition of the invention contains an onium salt.
In particular, when the other resin includes a polyimide precursor, the composition preferably includes an onium salt.
The type of onium salt is not particularly limited, but 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 the polymer.

Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded through a covalent bond. .
That is, the onium salt may be an inner salt having a cation part and an anion part in the same molecular structure, or an onium salt in which a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. Although it may be an intermolecular salt, it is preferably an intermolecular salt. Furthermore, in the composition of the present invention, the cation moiety or cation molecule and the anion moiety or anion molecule may be bonded by an ionic bond or may be dissociated.
The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

The onium salt used in the present invention may be a thermal base generator.
The thermal base generator refers to a compound that generates a base when heated, and includes, for example, an acidic compound that generates a base when heated to 40° C. or higher.

[Ammonium salt]
In the present invention, ammonium salt means a salt of an ammonium cation and an anion.

-Ammonium cation-
As the ammonium cation, a quaternary ammonium cation is preferred.
Moreover, as the ammonium cation, a cation represented by the following formula (101) is preferable.
In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to each other to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or an alkyl group having 6 to 6 carbon atoms. More preferably, it is an aryl group of 12. R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. Examples include carbonyl group and acyloxy group.
When at least two of R ¹ to R ⁴ are bonded together to form a ring, the ring may contain a heteroatom. Examples of the above-mentioned heteroatoms include nitrogen atoms.

The ammonium cation is preferably represented by either of the following formulas (Y1-1) and (Y1-2).

In formulas (Y1-1) and (Y1-2), R ¹⁰¹ represents an n-valent organic group, R ¹ has the same meaning as R ¹ in formula (101), and Ar ¹⁰¹ and Ar ¹⁰² each independently represent , represents an aryl group, and n represents an integer of 1 or more.
In formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon, benzene, or naphthalene.
In formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

-Anion-
The anion in the ammonium salt is preferably one selected from carboxylic acid anions, phenol anions, phosphate anions, and sulfate anions, and carboxylic acid anions are more preferable because they can achieve both stability and thermal decomposition of the salt. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably an anion of divalent or higher carboxylic acid having two or more carboxy groups, and more preferably an anion of divalent carboxylic acid. According to this aspect, the stability, curability, and developability of the composition can be further improved. In particular, by using a divalent carboxylic acid anion, the stability, curability, and developability of the composition can be further improved.

The carboxylic acid anion is preferably represented by the following formula (X1).
In formula (X1), EWG represents an electron-withdrawing group.

In this embodiment, the electron-withdrawing group means a group having a positive Hammett substituent constant σm. Here, σm is as described in the review by Yuho Tsuno, Journal of the Society of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965), p. 631-642. Note that the electron-withdrawing group in this embodiment is not limited to the substituents described in the above literature.
Examples of substituents in which σm is a positive value include CF ₃ group (σm=0.43), CF ₃ C(=O) group (σm=0.63), and HC≡C group (σm=0. 21), _CH2 =CH group (σm=0.06), Ac group (σm=0.38), MeOC(=O) group (σm=0.37), MeC(=O)CH=CH group ( σm=0.21), PhC(=O) group (σm=0.34), H ₂ NC(=O)CH ₂ group (σm=0.06), and the like. Note that Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same applies hereinafter).

EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, or a carboxy group, and Ar is an aromatic group. represents.

In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).
In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, -NR ^x -, and a combination thereof, and R ^x is , represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

Specific examples of carboxylic acid anions include maleic acid anions, phthalic acid anions, N-phenyliminodiacetic acid anions, and oxalic acid anions.

From the viewpoints that the cyclization of the specific resin is easily carried out at low temperature and the storage stability of the composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt contains a conjugate acid as an anion. It is preferable that the anion contains an anion whose pKa (pKaH) is 2.5 or less, and more preferably an anion whose pKa (pKaH) is 1.8 or less.
The lower limit of the above pKa is not particularly limited, but from the viewpoint of making it difficult for the generated base to be neutralized and improving the cyclization efficiency of specific resins, it is preferably -3 or more, and -2 or more. is more preferable.
The above pKa is described in Determination of Organic Structures by Physical Methods (Author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C. .; Compiled by: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Pr. ess, 1959). I can do it. For compounds that are not described in these documents, values calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software are used.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited thereto.

[Iminium salt]
In the present invention, iminium salt means a salt of an iminium cation and an anion. Examples of the anion include those similar to those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Iminium cation-
As the iminium cation, a pyridinium cation is preferred.
Further, as the iminium cation, a cation represented by the following formula (102) is also preferable.

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and at least two of R ⁵ to R ⁷ are each bonded to form a ring. may be formed.
In formula (102), R ⁵ and R ⁶ have the same meanings as R ¹ to R ⁴ in formula (101) above, and preferred embodiments are also the same.
In formula (102), R ⁷ is preferably bonded to at least one of R ⁵ and R ⁶ to form a ring. The ring may contain heteroatoms. Examples of the above-mentioned heteroatoms include nitrogen atoms. Moreover, as the above-mentioned ring, a pyridine ring is preferable.

The iminium cation is preferably one represented by one of the following formulas (Y1-3) to (Y1-5).
In formulas (Y1-3) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, R ⁵ has the same meaning as R ⁵ in formula (102), and R ⁷ represents R in formula (102). ⁷ , n represents an integer of 1 or more, and m represents an integer of 0 or more.
In formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon, benzene, or naphthalene.
In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

Specific examples of iminium salts include the following compounds, but the present invention is not limited thereto.

[Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include those similar to those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.
Moreover, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.
R ⁸ to R ¹⁰ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and It is more preferable that it is an aryl group, and even more preferable that it is a phenyl group.
R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. Examples include carbonyl group and acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as a substituent, more preferably a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms. More preferably, it has 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.

[Iodonium salt]
In the present invention, iodonium salt means a salt of an iodonium cation and an anion. Examples of the anion include those similar to those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Iodonium cation-
As the iodonium cation, a diaryliodonium cation is preferred.
Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and It is more preferable that it is an aryl group, and even more preferable that it is a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. Examples include carbonyl group and acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as a substituent, more preferably a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.

[Phosphonium salt]
In the present invention, phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include those similar to those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

-Phosphonium cation-
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation, a triarylmonoalkylphosphonium cation, and the like.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and It is more preferable that it is an aryl group, and even more preferable that it is a phenyl group.
R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. Examples include carbonyl group and acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as a substituent, more preferably a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.

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, even 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, further preferably 20% by mass or less, even more preferably 10% by mass or less, may be 5% by mass or less, and may be 4% by mass or less.
One type or two or more types of onium salts can be used. When two or more types are used, the total amount is preferably within the above range.

<Thermal base generator>
Compositions of the invention may also include a thermal base generator.
In particular, when the composition contains a polyimide precursor as the other resin, it is preferred that the composition contains a thermal base generator.
The thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt.
Other thermal base generators include nonionic thermal base generators.
Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

In formulas (B1) and (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 do not become hydrogen atoms at the same time. Further, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In addition, 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, this does not apply when the bonded carbon atom forms a carbonyl group, that is, when it forms an amide group together with a nitrogen atom.

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, and preferably a monocycle or a condensed ring in which two monocycles are condensed. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

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

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

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

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in Formula (B1), respectively.
Rb ¹³ is 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 carbon atoms, 3 to 12 carbon atoms) is more preferable), an aryl group (preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms), 7 to 12 are more preferable), and may have a substituent within the range that produces the effects of the present invention. Among these, Rb ¹³ is preferably an arylalkyl group.

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

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

Rb ¹¹ and Rb ¹² have the same meanings 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 carbon atoms, even more preferably 1 to 3 carbon atoms), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). more preferably 2 to 3 carbon atoms), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms), arylalkyl group (preferably 7 to 23 carbon atoms, 7 carbon atoms 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, even 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 carbon atoms) is more preferable), an aryl group (preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms), 7 to 12 are more preferred), and aryl groups are particularly preferred.

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

Among the above-mentioned onium salts, 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 type or two or more types of thermal base generators can be used. When two or more types are used, the total amount is preferably within the above range.

<Crosslinking agent>
The photosensitive resin composition of the present invention preferably contains a crosslinking agent.
Examples of crosslinking agents include radical crosslinking agents and other crosslinking agents.

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

The radical crosslinking agent may be any compound having one or more ethylenically unsaturated bonds, but it is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Moreover, from the viewpoint of film strength of the resulting pattern (cured film), the photosensitive resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical crosslinking agent. The compound having three 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 more preferably a compound having 3 to 6 ethylenically unsaturated bonds. More preferred are compounds having the following.
Further, the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more groups containing the above ethylenically unsaturated bond, more preferably a compound having 3 to 15 groups, A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
In addition, from the viewpoint of film strength of the obtained pattern (cured film), 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. It is also preferable to include a compound.

The molecular weight of the radical crosslinking 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 crosslinking agent is preferably 100 or more.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. These 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 nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and 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 furthermore, halogen groups Substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as or tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, as another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid mentioned above is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, or the like. As a specific example, the descriptions in paragraphs 0113 to 0122 of JP-A No. 2016-027357 can be referred to, and the contents thereof are incorporated into the present specification.

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

In addition, preferable radical crosslinking agents other than those mentioned above include those having a fluorene ring and having an ethylenically unsaturated bond, as described in JP-A No. 2010-160418, JP-A No. 2010-129825, Japanese Patent No. 4364216, etc. It is also possible to use compounds having two or more groups and cardo resins.

Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, and those described in Japanese Patent Publication No. 02-025493. Vinylphosphonic acid compounds and the like can also be mentioned. Further, compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, Japan Adhesive Association Journal 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 JP2015-034964A and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents of these are herein incorporated by reference. incorporated into the book.

In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then converting it into (meth)acrylate, which are described in JP-A No. 10-062986 as formulas (1) and (2) together with specific examples thereof, can also be used. It can be used as a radical crosslinking agent.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as a radical crosslinking agent, and the contents thereof are incorporated herein.

Examples of radical crosslinking agents include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). ), A-TMMT: manufactured by Shin Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) ) acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and their (meth)acryloyl groups via ethylene glycol residues or propylene glycol residues. A structure in which both are bonded together is preferred. These oligomeric types can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer; SR-209, manufactured by Sartomer, a difunctional methacrylate having four ethyleneoxy chains; 231, 239, DPCA-60, a hexafunctional acrylate with 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate with 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 Industry Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), Blenmar PME400 (NOF Corporation), etc. Can be mentioned.

As the radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Furthermore, as a radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do that.

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. A radical crosslinking agent having the following is more preferable. Particularly preferably, in the radical crosslinking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound that is Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, it will be excellent in handling during production and furthermore, it will be excellent in developability. Moreover, it has good polymerizability. In addition, from the viewpoint of development speed in the case of alkaline development, the preferable acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. The above acid value is measured according to the description in JIS K 0070:1992.

In the photosensitive resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured film). Examples of monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, and 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. Preferably used are 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. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure. Furthermore, from the viewpoint of pattern resolution and film stretchability, it is also preferable to use bifunctional methacrylate or acrylate.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene Glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexane Diol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, Use EO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates with urethane bonds, and bifunctional methacrylates with urethane bonds. be able to. These can be used as a mixture of two or more types, if necessary.

When containing a radical crosslinking agent, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and 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 used in combination. When two or more types are used together, it is preferable that the total amount falls within the above range.

<Other crosslinking agents>
The photosensitive resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned radical crosslinking agents, which form covalent bonds with other compounds in the composition or their reaction products through the sensitization of the above-mentioned photosensitizers. It is preferable that the compound has a plurality of groups in its molecule that promote the formation reaction, and the reaction that forms a covalent bond with other compounds in the composition or the reaction product thereof is facilitated by the action of an acid or base. Compounds having a plurality of groups promoted by in the molecule are preferred.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator that is a photosensitizer in an exposure process such as a first area exposure process and a second area exposure process.
The other crosslinking agent is preferably a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom. A compound having a structure directly bonded to is more preferable.
Other crosslinking agents include, for example, reacting an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine with formaldehyde or formaldehyde and alcohol to convert the hydrogen atom of the amino group into a methylol group or an alkoxymethyl group. Examples include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Moreover, an oligomer formed by self-condensation of the methylol groups of these compounds may also be used.
As the above amino group-containing compound, a crosslinking agent using melamine is a melamine crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is a urea crosslinking agent, and a crosslinking agent using alkylene urea is an alkylene urea crosslinking agent. A crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
Among these, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and a glycoluril-based crosslinking agent and melamine, which will be described later. It is more preferable to include at least one compound selected from the group consisting of crosslinking agents.

Specific examples of the melamine crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of urea-based crosslinking 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, Propoxymethylated glycoluril, triproxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril, etc. glycoluril crosslinking agent;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea,
Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl ethylene urea-based crosslinking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxy methyl 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 crosslinking agents such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

Specific examples of benzoguanamine-based crosslinking 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 Examples include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is added to 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 crosslinking agents, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Yokuzai Kogyo 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 (the above, Honshu (manufactured by Kagaku Kogyo Co., Ltd.), Nikalak (registered trademark, hereinafter the same) MX-290, Nikalak MX-280, Nikalak MX-270, Nikalak MX-279, Nikalak MW-100LM, Nikalak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ), etc.

It is also preferable that the photosensitive resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.

[Epoxy compound (compound with epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200° C. or lower, and no dehydration reaction due to crosslinking occurs, so membrane shrinkage is less likely to occur. Therefore, containing an epoxy compound is effective in curing the photosensitive resin composition at low temperatures and suppressing warpage.

Preferably, the epoxy compound contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group means one in which the number of ethylene oxide repeating units is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, and hexamethylene glycol diglycidyl ether. , alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin such as trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; epoxy group such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, silicone containing silicone. 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, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740, Recare Resin (registered trademark) BEO-20E (or more products) (manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (product names, new Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all product names, manufactured by ADEKA Co., Ltd.), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Cervinas B0134 , B0177 (all product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC- 2000-L, 201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

[Oxetane compound (compound having an oxetanyl group)]
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, Examples include 3-ethyl-3-(2-ethylhexylmethyl)oxetane and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. As a specific example, the Aronoxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these alone, Alternatively, two or more types may be mixed.

[Benzoxazine compound (compound having a benzoxazolyl group)]
A benzoxazine compound is preferable because it does not generate outgassing during curing due to a crosslinking reaction derived from a ring-opening addition reaction, and furthermore, it reduces thermal shrinkage and suppresses the occurrence of warpage.

Preferred examples of benzoxazine compounds include Ba-type benzoxazine, B-m-type benzoxazine, Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and Polymer. Examples include benzoxazine adducts of hydroxystyrene resins and phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 0.5 to 15% by weight, and particularly preferably 1.0 to 10% by weight. Only one type of other crosslinking agent may be contained, or two or more types thereof may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total amount is within the above range.

<Compounds with sulfonamide structure, compounds with thiourea structure>
From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the photosensitive resin composition of the present invention is composed of a compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. Preferably, it further contains at least one compound.

[Compound with sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).
In formula (S-1), R represents a hydrogen atom or an organic group, R may be combined with another structure to form a ring structure, and * each independently represents a bonding site with another structure. represent.
The above R is preferably the same group as R ² in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ are bonded to each other. It may form a ring structure.
It is preferable that R ¹ , R ² and R ³ are each independently a monovalent organic group.
Examples of R ¹ , R ² and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, Examples include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and a combination of two or more thereof.
The alkyl group mentioned above is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, and 2-ethylhexyl group.
The above-mentioned cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and pentoxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The above aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The above aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl group, tolyl group, xylyl group, and naphthyl group.
The above heterocyclic groups include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring. , a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, a triazine ring, and other groups in which one hydrogen atom is removed from a heterocyclic structure.

Among these, compounds in which R ¹ is an aryl group, and R ² and R ³ are each independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1 -Sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethyl Examples include methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compound with thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).
In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ may be combined to form a ring structure, and R ⁴ is * may be bonded to another structure to form a ring structure, R ⁵ may be bonded to another structure to which * is bonded to form a ring structure, and each * independently represents the binding site with the structure of

It is preferable that R ⁴ and R ⁵ are each independently a hydrogen atom.
Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, Examples include an allyl group, a vinyl group, a heterocyclic group, and a combination of two or more of these groups.
The alkyl group mentioned above is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, and 2-ethylhexyl group.
The above-mentioned cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and pentoxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The above aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The above aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, tolyl group, xylyl group, and naphthyl group.
The above heterocyclic groups include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring. , a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, a triazine ring, and other groups in which one hydrogen atom is removed from a heterocyclic structure.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ are bonded to each other to form a ring structure. You can.

In formula (T-2), R ⁴ and R ⁵ have the same meanings as R ⁴ and R ⁵ in formula (T-1), and preferred embodiments are also the same.
In formula (T-2), R ⁶ and R ⁷ are each independently preferably a monovalent organic group.
In formula (T-2), the preferred embodiments of the monovalent organic group in R ⁶ and R ⁷ are the same as the preferred embodiments of the monovalent organic group in R ⁴ and R ⁵ in formula (T-1). .

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'- Diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethyl Examples include thiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure with respect to the total mass of the photosensitive resin composition of the present invention is preferably 0.05 to 10% by mass, and 0.1 to 5% by mass. %, and even more preferably 0.2 to 3% by mass.
The photosensitive resin composition of the present invention may contain only one kind of compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more kinds. When only one type of compound is included, the content of the compound is preferably within the above range, and when two or more types are included, the total amount thereof is preferably within the above range.

<Migration inhibitor>
It is preferable that the photosensitive resin composition of the present invention further contains a migration inhibitor. By including a migration inhibitor, it becomes possible to effectively suppress metal ions originating from the metal layer (metal wiring) from moving into the photocurable layer.

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

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

Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and the compounds described in JP-A-2011-059656. Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116, and 0118 of JP2012-194520A, compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. 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, based on the total solid content of the photosensitive resin composition, and 0. The amount is more preferably .05 to 2.0% by weight, and even more preferably 0.1 to 1.0% by weight.

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

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

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, 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-nitrosophenylhydroxyamine cerous salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy) -2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbanate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxyl Amine ammonium salts and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817A and the compound described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

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

When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0% by mass based on the total solid content of the photosensitive resin composition of the present invention. It is preferably from 0.01 to 5% by weight, even more preferably from 0.02 to 3% by weight, particularly preferably from 0.05 to 2.5% by weight.

The number of polymerization inhibitors may be one, or two or more. When there are two or more types of polymerization inhibitors, it is preferable that the total is 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, etc. Examples of metal adhesion improvers include silane coupling agents, aluminum adhesion aids, titanium adhesion aids, compounds with a sulfonamide structure and thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, etc. can be mentioned.

Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP2014-191002, and paragraphs of WO 2011/080992. Compounds described in paragraphs 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP 2014-191252, compounds described in paragraphs 0045 to 0052 of JP 2014-041264, and compounds described in WO 2014/097594. Examples include the compounds described in paragraph 0055. Furthermore, 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 compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Furthermore, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP2014-186186A and sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used. . Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Examples include propyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.
Examples of the aluminum adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. By setting it above the above-mentioned lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it below the above-mentioned upper limit, the heat resistance and mechanical properties of the pattern become good. There may be only one type of metal adhesion improver, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Sensitizer>
The photosensitive resin composition of the present invention may contain a sensitizer. A sensitizer absorbs specific actinic radiation and becomes electronically excited. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 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-diethylaminocoumarin Coumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl) aminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4 '-dimethylacetanilide and the like.
Moreover, a sensitizing dye may be used as the sensitizer.
For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357A can be referred to, and the contents thereof are incorporated herein.

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

<Other additives>
The photosensitive resin composition of the present invention may optionally contain various additives, such as surfactants, chain transfer agents, higher fatty acid derivatives, inorganic particles, curing agents, etc., as long as the effects of the present invention can be obtained. A curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent, etc. can be added. When blending these additives, the total blending amount is preferably 3% by mass or less based on the solid content of the photosensitive resin composition.
[Surfactant]
Various types of surfactants may be added to the curable resin composition of the present invention from the viewpoint of further improving coating properties. As the surfactant, various types of surfactants can be used, such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The following surfactants are also preferred. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol %) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repeats of each repeating unit.
Further, as the surfactant, compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
Examples of the fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (Asahi Glass ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of JP-A 2011-132503 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples include compounds described in JP-A No. 2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A No. 2010-164965, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. Can be mentioned.
The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving, and has good solubility in the composition.
Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (manufactured by BYK Chemie Co., Ltd.), and the like.
Examples of the hydrocarbon surfactant include Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin D-3605. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Examples include Pionin P-4050-T (manufactured by Takemoto Yushi Co., Ltd.).
Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.) (manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) Examples include.
Specifically, the cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Kagaku Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. The amount is preferably from 0.005 to 1.0% by mass, more preferably from 0.005 to 1.0% by mass. The number of surfactants may be one, or two or more. When there are two or more types of surfactants, it is preferable that the total is within the above range.

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

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

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass based on 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 weight, more preferably 1 to 5 parts by weight. The number of chain transfer agents may be one, or two or more. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.

[Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the photosensitive resin composition of the present invention is prepared by adding a higher fatty acid derivative such as behenic acid or behenic acid amide to the photosensitive resin composition during the drying process after coating. It may be unevenly distributed on the surface of an object.

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

一般式（３）中、Ｒ^５は水素原子または炭素数２以上のアルキル基を表し、Ｒ^６は炭素数２以上のアルキレン基を表す。Ｒ^７は、炭素数２以上のアルキレン基、Ｏ原子、およびＮ原子のうち少なくともいずれかを含む１～４価の有機基を示す。ｋは１～４の整数を示す。
一般式（３）で表される化合物は、樹脂の脂肪族基やフェノール性水酸基の酸化劣化を抑制する。また、金属材料への防錆作用により、金属酸化を抑制することができる。
樹脂と金属材料に同時に作用できるため、ｋは２～４の整数がより好ましい。Ｒ７としては、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシル基、カルボニル基、アリル基、ビニル基、複素環基、－Ｏ－、－ＮＨ－、－ＮＨＮＨ－、それらを組み合わせたものなどが挙げられ、さらに置換基を有していてもよい。この中でも、現像液への溶解性や金属密着性の点から、アルキルエーテル、－ＮＨ－を有することが好ましく、樹脂との相互作用と金属錯形成による金属密着性の点から－ＮＨ－がより好ましい。
下記一般式（３）で表される化合物は、例としては以下のものが挙げられるが、下記構造に限らない。

酸化防止剤の添加量は、樹脂に対し、０．１～１０質量部が好ましく、０．５～５質量部がより好ましい。添加量が０．１質量部より少ない場合は、硬化後の膜の伸度特性や金属材料に対する密着性向上の効果が得られにくく、また１０質量部より多い場合は、感光剤との相互作用により、樹脂組成物の感度低下を招く恐れがある。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative should be 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition of the present invention. is preferred. There may be only one type of higher fatty acid derivative, or two or more types may be used. When there are two or more types of higher fatty acid derivatives, it is preferable that the total is within the above range.
[Inorganic particles]
The resin composition of the present invention may also contain inorganic particles. Specifically, the inorganic particles can include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, particularly 0.04 to 0.5 μm. preferable.
By containing a large amount of inorganic particles, the mechanical properties of the cured film may deteriorate. Furthermore, if the average particle diameter of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.
[Ultraviolet absorber]
The composition of the present invention may also contain a UV absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and examples of benzophenone UV absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Examples include hydroxy-4-octoxybenzophenone. In addition, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3', '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole and the like.
Examples of substituted acrylonitrile ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Furthermore, examples of triazine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) Mono(hydroxyphenyl)triazine compounds such as -1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine ;2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl -4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2 ,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl) )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4 Examples include tris(hydroxyphenyl)triazine compounds such as -(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.
In the present invention, the various types of ultraviolet absorbers described above may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the content of the ultraviolet absorber is 0.001% by mass based on the total solid mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
[Organotitanium compound]
The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
Examples of organic titanium compounds that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of organic titanium compounds are shown in I) to VII) below.
I) Titanium chelate compound: Among these, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition is good and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate) , titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethyl phenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)] butoxide}], etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agent: for example, isopropyl tridodecyl benzenesulfonyl titanate.
Among these, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred for better chemical resistance. This is preferable from the viewpoint of performance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H -pyrrol-1-yl)phenyl)titanium is preferred.
When blending an organic titanium compound, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the cyclized resin precursor. . When the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the composition has excellent storage stability.
〔Antioxidant〕
The composition of the invention may also contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Further, as the antioxidant, a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Further, as the antioxidant, phosphorus-based antioxidants can also be suitably used. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl )oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.). Further, as the antioxidant, compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
The composition of the present invention may also contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.). Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by the following general formula (3). .

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ⁶ represents an alkylene group having 2 or more carbon atoms. R ⁷ represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. k represents an integer from 1 to 4.
The compound represented by general formula (3) suppresses oxidative deterioration of aliphatic groups and phenolic hydroxyl groups of the resin. Moreover, metal oxidation can be suppressed by the rust-preventing effect on metal materials.
Since k can act on resin and metal materials simultaneously, it is more preferable that k is an integer of 2 to 4. R7 is an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, - Examples include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have an alkyl ether or -NH- from the viewpoint of solubility in a developer and metal adhesion, and -NH- is preferable from the viewpoint of metal adhesion due to interaction with the resin and metal complex formation. preferable.
Examples of the compound represented by the following general formula (3) include, but are not limited to, the following structures.

The amount of antioxidant added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on the resin. If the amount added is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation characteristics of the film after curing or the adhesion to metal materials, and if it is more than 10 parts by mass, it may cause interaction with the photosensitizer. This may lead to a decrease in the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls 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 during storage conditions and reducing the porosity of the storage container during storage.

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

Furthermore, methods for reducing metal impurities unintentionally included in the photosensitive resin composition of the present invention include selecting raw materials with a low metal content as raw materials constituting the photosensitive resin composition of the present invention. Methods include filtering the raw materials constituting the photosensitive resin composition of the invention, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination 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 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm, from the viewpoint of wiring corrosion resistance. More preferably less than ppm. Among these, 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. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is each within the above range.
Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

As a container for storing the photosensitive resin composition of the present invention, a conventionally known container can be used. In addition, for the purpose of suppressing the contamination of impurities into raw materials and photosensitive resin compositions, storage containers include multilayer bottles whose inner walls are made of six types and six layers of resin, and six types of resins and seven layers. It is also preferred to use bottles with a layered structure. Examples of such a container include the container described in JP-A No. 2015-123351.

<Applications of photosensitive resin composition>
The photosensitive resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer.
In addition, it can also be used to form an insulating film of a semiconductor device, a stress buffer film, etc.

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

Further, in order to remove foreign substances such as dust and fine particles from the photosensitive resin composition, it is preferable to perform filtration using a filter. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, the thickness is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials may be used in combination. Additionally, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be used. Alternatively, filtration may be performed under pressure. When filtration is performed under pressure, the pressure to be applied is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, it is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, and even more preferably 0.05 MPa or more and 0.7 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise stated.

<Synthesis example 1>
[Synthesis of polyimide precursor PIP-1]
9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride, oxydiphthalic dianhydride with removal of moisture in a dry reactor equipped with a flat-bottomed joint fitted with a stirrer, condenser and internal thermometer. 10.0 g (32.25 mmol) of the compound was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60° C. for 18 hours. Then, 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 obtain a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the resulting clear solution over a period of 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. Next, the obtained polyimide precursor resin was dried at 45° C. for 3 days under reduced pressure to obtain polyimide precursor PIP-1.

<Synthesis example 2>
[Synthesis of polyimide precursor PIP-2]
Polyimide precursor PIP-2 was obtained in the same manner as in Synthesis Example 1, except that 4,4'-diaminodiphenyl ether was changed to an equimolar amount of 1,6-diaminohexane.

<Synthesis example 3>
[Synthesis of polyimide precursor PIP-3]
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, 0.05g of hydroquinone, 10.7g of pyridine, and 140g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60°C for 18 hours to form 4,4'-oxydiphthalic acid. A diester with 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10° C. and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes while maintaining the temperature at −10±4° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated by adding 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5,000 rpm. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain polyimide precursor PIP-3.

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

<Synthesis example 5>
[Synthesis of polybenzoxazole precursor PBP-1]
73.25 g (0.200 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane (Bis-AP) was placed in a three-necked flask equipped with a thermometer, stirrer, and nitrogen inlet tube. -AF (manufactured by Central Glass Co., Ltd.), 31.64 g (0.400 mol) of pyridine, and 293 g of NMP were added. This was stirred at room temperature and then cooled to -15°C in a dry ice/methanol bath. To this solution, while maintaining the reaction temperature between -5°C and -15°C, 30.11 g (0.144 mol) of 1,4-cyclohexanedicarboxylic acid dichloride in a 30% by mass NMP solution and 3.83 g (0.14 mol) of 1,4-cyclohexanedicarboxylic acid dichloride were added. A mixed solution of 016 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 96.25 g of NMP was added dropwise. After the addition was completed, the resulting mixture was stirred at room temperature for 16 hours.
Next, this reaction solution was cooled to below -5°C in an ice/methanol bath, and while maintaining the reaction temperature below -0°C, 9.59 g (0.090 mol) of butyryl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. ) and 34.5 g of NMP were added dropwise. After the addition was completed, stirring was continued for an additional 16 hours.
The reaction solution was diluted with 550 g of NMP and poured into 4 L of a vigorously stirred 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 at 50° C. for 2 days under vacuum 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 a 500 mL eggplant flask, and the mixture was 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 (manufactured by Wako Pure Chemical Industries, Ltd.) were added. ) and stirred at room temperature for 1.5 hours. The resulting solution was diluted by adding 0.37 g of triethylamine and 150 g of NMP.
The resulting solution was poured into 2 L of a vigorously stirred 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 at 50° C. for 2 days under vacuum to obtain polybenzoxazole (PBO) precursor PBP-1.

<Examples and comparative examples>
In each Example, the components listed in Tables 1 to 3 below were mixed to obtain each photosensitive resin composition. Further, in a comparative example, the components listed in Table 3 below were mixed to obtain a comparative composition.
Specifically, the contents of the components listed in Tables 1 to 3 were the amounts listed in "parts by mass" in Tables 1 to 3. Further, in each composition, the content of the solvent was such that the solid content concentration of the composition was the value shown in Tables 1 to 3.
The obtained photosensitive resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a filter pore size of 0.8 μm.
Furthermore, in Tables 1 to 3, the description "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 1 to 3 are as follows.

〔resin〕
・PIP-1 to PIP-3: PIP-1 to PIP-3 synthesized above
・PI-1: PI-1 synthesized above
・PBP-1: PBP-1 synthesized above

[Radical crosslinking agent]
・B-1: Tetraethylene glycol dimethacrylate ・B-2: Dipentaerythritol hexaacrylate ・B-3: Light ester BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd.)
・B-4: SR209 (manufactured by Sartomer Japan Co., Ltd.)

[Photosensitizer]
・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: Compound with the following structure

〔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: N-[3-(triethoxysilyl)propyl]maleic acid monoamide ・D-5: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Polymerization inhibitor]
・E-1: 2-nitroso-1-naphthol ・E-2: 4-methoxyphenol ・E-3: Compound with the following structure ・E-4: 4-methoxy-1-naphthol ・E-5: p-benzoquinone

[Sensitizer]
・F-1: Ethyl 7-(diethylamino)coumarin-3-carboxylate ・F-2: N-phenyldiethanolamine

[Migration inhibitor]
・G-1: 1H-tetrazole

[Acid crosslinking agent (other crosslinking agent)]
・H-1: Nikarak MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

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

〔Additive〕
・J-1: 1,3-dibutylthiourea

[Thermal base generator]
・K-1: Compound with the following structure

[Surfactant]
・L-1: F-554 (manufactured by DIC Corporation)

〔solvent〕
・S-1: N-methyl-2-pyrrolidone ・S-2: Ethyl lactate ・S-3: γ-butyrolactone ・S-4: Dimethyl sulfoxide In Tables 1 to 3, the description in the "Ratio" column is as follows: The content (mass%) of each solvent with respect to the total mass of the solvent is shown.

<Evaluation>
[Evaluation of pattern shape]
In each Example and Comparative Example, each photosensitive resin composition or comparative composition was applied (coated) in a layer on a silicon wafer by a spin coating method to form a photoresist film.
In each Example and Comparative Example, the silicon wafer to which the above photoresist film was applied was dried on a hot plate at 80°C for 3 minutes, and the "film thickness (μm)" column of Tables 1 to 3 was printed on the silicon wafer. A photoresist film having the thickness described was formed.
The formed photoresist film on the silicon wafer was heated using a semiconductor laser having the laser output listed in the "Laser output (W)" column and the exposure wavelength listed in the "Exposure wavelength (nm)" column in Tables 1 to 3. It was exposed using. For example, in Example 1, all four exposures were performed at a laser output of 0.6W. In Example 20, the first region exposure step was performed at an output of 0.6 W, the second region exposure step was performed at an output of 1.2 W, the third region exposure step was performed at an output of 1.8 W, and the fourth region was Each exposure step was performed at a power of 1.8W. In addition, in the examples in which "HP" was written in the "Exposure wavelength (nm)" column, exposure was performed using a high-pressure mercury lamp.
Exposure was performed at the number of times described in the "Number of exposures" column in Tables 1 to 3 and at the intervals described in "Interval (seconds)." For example, in Example 1, a total of four exposures (quadruple exposure) were performed with intervals of 10 seconds each (time during which no exposure was performed). Further, in Example 5, exposure was performed a total of four times while changing the interval to 5 seconds, 10 seconds, and 15 seconds.
In each Example or Comparative Example, each exposure step was performed with the same amount of exposure. In addition, when a high-pressure mercury lamp was used for exposure, the above exposure amount was the i-line exposure amount.
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 the above exposure, in the examples described as "A" in the "Developer" column of Tables 1 to 3, development was performed using cyclopentanone for 60 seconds and propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. After rinsing, a line and space pattern of the photosensitive film was obtained. In the examples described as "B" in the "Developer" column of Tables 1 to 3, development was performed using a 2.5% by mass tetramethylammonium hydroxide aqueous solution for 60 seconds, and rinsed with pure water for 20 seconds. A line and space pattern of the photoresist film after exposure was obtained. In Example 11, the above development was performed after heating at 100°C for 60 seconds on a hot plate.Then, the developed pattern and the silicon wafer on which the above pattern was formed were heated at 10°C under a nitrogen atmosphere. After increasing the temperature at a heating rate of /min and reaching the temperature listed in the "Cure temperature (°C)" column of Tables 1 to 3, A silicon wafer on which a pattern was formed was obtained by curing for the stated period of time.
The silicon wafer on which the obtained pattern (line and space pattern) was formed was cut perpendicularly to the line and space pattern to expose the cross section of the pattern. The pattern cross section of the line and space pattern was observed using an optical microscope at a magnification of 200 times, and the cross-sectional shape of the pattern was evaluated.
Specifically, in each Example and Comparative Example, the taper angle between the surface of the silicon wafer (substrate surface) and the side surface of the pattern was measured and evaluated according to the following evaluation criteria. It can be said that the closer the taper angle is to 90°, the better the pattern shape.
-Evaluation criteria-
A: The taper angle was 85° or more and 95° or less.
B: The taper angle was 80° or more and less than 85°, or more than 95° and less than 100°. C: The taper angle was less than 80° or 100° or more.

[Resolution evaluation]
In each Example and Comparative Example, a photoresist film having the thickness listed in the "Film Thickness (μm)" column of Tables 1 to 3 was formed on a silicon wafer by the same method as in the evaluation of pattern shape.
The photoresist film formed on the silicon wafer was exposed to light in the same manner as in the evaluation of the pattern shape, except that a photomask in which a line and space pattern was formed from 5 μm to 25 μm in 1 μm increments was used as a photomask.
After the above exposure, each photoresist film was developed and heated in the same manner as in the evaluation of the pattern shape to obtain a silicon wafer on which a pattern was formed.
The developed pattern was observed using a scanning electron microscope (SEM) to determine the minimum line width.
Evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in Tables 1 to 3. It can be said that the smaller the minimum line width is, the better the resolution is.

-Evaluation criteria-
A: The minimum line width is less than 10 μm. B: The minimum line width is 10 μm or more and less than 20 μm. C: The minimum line width is 20 μm or more, or a pattern having a line width with sharp edges cannot be obtained. Ta.

The pattern forming method according to Comparative Example 1 does not include the second exposure step and performs exposure only once. It can be seen that in such an example, the pattern shape is inferior.

<Example 101>
The photosensitive resin composition used in Example 1 was applied in a layered manner by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 80° C. for 3 minutes. After forming a photocurable layer with a film thickness of 20 μm, a total of four exposures were performed using a semiconductor laser with a laser output of 0.6 W, with an interval of 10 seconds (time during which no exposure was performed) in between. Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, a pattern of layers was obtained by developing with cyclopentanone for 60 seconds and rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds.
Next, the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., it was maintained for 120 minutes to be cured to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for rewiring layer had excellent insulation properties.
Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, it was confirmed that they operated without problems.

Claims (12)

a first area exposure step of selectively exposing a first area, which is a partial area of a photosensitive film made of a photosensitive resin composition;
a second region exposure step of selectively exposing a second region, which is a partial region of the photoresist film after the first region exposure step;
a developing step of developing the photoresist film after the second area exposure step;
At least some areas included in the first area and at least some areas included in the second area are common areas,
The photosensitive resin composition contains at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, and a photosensitizer,
Among the steps of exposing a part of the photoresist film included before the development step, it is the time from the end of one exposing step to the start of another exposing step, and The time not including the step of exposing to light is 0.1 seconds or more,
The ratio of the total area of the area exposed twice or more to the total area of the area exposed at least once is 100%,
The photosensitizer is a photoradical polymerization initiator or a photoacid generator,
When the photosensitive agent is a radical photopolymerization initiator, the resin has a radically polymerizable group, or the photosensitive resin composition further contains a radical crosslinking agent. The photosensitive resin composition contains a photoradical polymerization initiator as the photosensitizer, and the resin has a radical polymerizable group, or contains a photoacid generator as the photosensitizer, and the resin has an acid-decomposable group, or has at least one group selected from the group consisting of a methylol group and an alkoxymethyl group as a crosslinking agent , an epoxy compound, an oxetane compound, and a benzoxazine compound. The pattern forming method according to claim 1, comprising at least one compound selected from the following. a third region exposure step of selectively exposing a third region which is a partial region of the photoresist film after the second region exposure step; and a third region which is a partial region of the photoresist film after the third region exposure step. a fourth region exposure step of selectively exposing a certain fourth region, the developing step is a step of developing the photoresist film after the fourth region exposure step, and at least a portion included in the third region and at least a part of the region included in the first region, the second region, and the fourth region, and at least a part of the region included in the fourth region 3. The pattern forming method according to claim 1, wherein the region and at least some regions included in any one of the first region, the second region, and the third region are common regions. The pattern forming method according to any one of claims 1 to 3, wherein the exposure wavelength in the first area exposure step and the second area exposure step is 300 to 450 nm. The pattern forming method according to any one of claims 1 to 4, wherein the photosensitive film made of the photosensitive resin composition has a thickness of 10 μm or more. The pattern forming method according to any one of claims 1 to 5, wherein the development in the development step is performed using an organic solvent as a developer. Pattern formation according to any one of claims 1 to 6, wherein the ratio of the area of the area included in both the first area and the second area to the total area of the first area is 100%. Method. The pattern forming method according to any one of claims 1 to 7, wherein the resin is a polyimide precursor. The pattern forming method according to any one of claims 1 to 8, wherein the photosensitive resin composition further contains a sensitizer. A photosensitive resin composition used for forming the photosensitive film in the pattern forming method according to any one of claims 1 to 9. A method for producing a laminate, comprising the pattern forming method according to any one of claims 1 to 9. A method for manufacturing an electronic device, comprising the method for forming a pattern according to any one of claims 1 to 9, or the method for manufacturing a laminate according to claim 11.