JP7261882B2 - Thermosetting photosensitive composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermosetting photosensitive composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.

Resins such as polyimide and polybenzoxazole are used in various applications because of their excellent heat resistance and insulating properties. The use is not particularly limited, but in the case of a semiconductor device for mounting, it can be used as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film or coverlay for flexible substrates.

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

For example, Patent Document 1 discloses a photosensitive resin composition containing (a) a polyimide resin or its precursor, (b) a quinonediazide compound, (c) a solvent and (d) a surfactant, wherein (d ) The surfactant contains (d1) a silicone surfactant and (d2) a fluorine atom-containing surfactant, and the content of (d1) in the photosensitive resin composition is X% by mass, and the content of (d2) When the amount is Y mass%, X > Y (Y ≠ 0), and (d) the total amount of the surfactant is 0.005 mass% or more and 0.10 mass% or less in the photosensitive resin composition Certain photosensitive resin compositions are described.

JP 2010-243748 A

When a cured film is produced by applying a thermosetting photosensitive composition containing at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors to a substrate, Other layers such as other thermosetting photosensitive layers may be further formed on the resulting cured film.
Moreover, as a substrate to which such a thermosetting photosensitive composition is applied, a non-uniform substrate such as having steps may be used.
Therefore, when the thermosetting photosensitive composition is applied to a non-uniform substrate such as having a step to prepare a cured film, and another layer is further formed on the obtained cured film It is desired to provide a thermosetting photosensitive composition that suppresses the occurrence of defects in other layers.

The present invention produces a cured film by applying it to a non-uniform substrate, and even when another layer is further formed on the obtained cured film, the occurrence of defects in other layers is suppressed. A thermosetting photosensitive composition, a cured film obtained by curing the thermosetting photosensitive composition, a laminate containing the cured film, a method for producing the cured film, and the cured film or the laminate An object of the present invention is to provide a semiconductor device comprising:

上記式（１）中、γ_ｓ ^ｄは硬化膜の表面自由エネルギーの分散成分を、γ_ｓ ^ｈは硬化膜の表面自由エネルギーの極性成分を、γ_L ^ｄは水又はジヨードメタンの表面自由エネルギーの分散成分を、γ_L ^ｈは水又はジヨードメタンの表面自由エネルギーの極性成分を、γ_L ^ｔоｔaｌは水又はジヨードメタンの表面自由エネルギーを、ｃоｓθは水又はジヨードメタンの接触角を、それぞれ表す；
ここで、表面自由エネルギーは分散成分と極性成分の和で表され、水の表面自由エネルギーの分散成分は２１．７ｍＪ／ｍ^２、水の表面自由エネルギーの極性成分は５０．８ｍＪ／ｍ^２、ジヨードメタンの表面自由エネルギーの分散成分は４８．１ｍＪ／ｍ^２、ジヨードメタンの表面自由エネルギーの極性成分は１．３ｍＪ／ｍ^２とする。
＜２＞ 上記界面活性剤の含有量が組成物の全質量に対して０．１質量％超である、＜１＞に記載の熱硬化性感光性組成物。
＜３＞ 上記界面活性剤の含有量が組成物の全質量に対して０．００５質量％未満である、＜１＞に記載の熱硬化性感光性組成物。
＜４＞ 上記界面活性剤がフッ素原子及びケイ素原子を有しない界面活性剤を含む、＜１＞～＜３＞のいずれか１つに記載の熱硬化性感光性組成物。
＜５＞ 上記組成物中の炭化水素系界面活性剤の含有量が上記界面活性剤の総含有量に対して５０質量％以上である、＜１＞～＜４＞のいずれか１つに記載の熱硬化性感光性組成物。
＜６＞ 上記樹脂がポリイミド及びポリイミド前駆体よりなる群から選ばれた少なくとも一種の樹脂を含む、＜１＞～＜５＞のいずれか１つに記載の熱硬化性感光性組成物。
＜７＞ スリットコート法による熱硬化性感光層の形成に用いられる、＜１＞～＜６＞のいずれか１つに記載の熱硬化性感光性組成物。
＜８＞ スピンコート法による熱硬化性感光層の形成に用いられる、＜１＞～＜６＞のいずれか１つに記載の熱硬化性感光性組成物。
＜９＞ 再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜８＞のいずれか１つに記載の熱硬化性感光性組成物。
＜１０＞ ＜１＞～＜９＞のいずれか１つに記載の熱硬化性感光性組成物を硬化してなる硬化膜。
＜１１＞ ＜１０＞に記載の硬化膜を２層以上含み、上記硬化膜同士のいずれかの間に金属層を含む積層体。
＜１２＞ ＜１＞～＜９＞のいずれか１つに記載の熱硬化性感光性組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
＜１３＞ 上記膜を露光する露光工程及び上記膜を現像する現像工程を含む、＜１２＞に記載の硬化膜の製造方法。
＜１４＞ 上記膜を、５０～４５０℃で加熱する加熱工程を含む、＜１２＞又は＜１３＞に記載の硬化膜の製造方法。
＜１５＞ ＜１０＞に記載の硬化膜又は＜１１＞に記載の積層体を含む、半導体デバイス。Examples of representative embodiments of the present invention are provided below.
<1> A thermosetting photosensitive composition used for forming a thermosetting photosensitive layer,
at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors;
photosensitizer,
a surfactant, and
contains solvents,
The surface free energy of the cured film A below and the surface free energy of the cured film B below calculated using the following formula (1) from the contact angle of water and the contact angle of diiodomethane on the surface of the cured film A below and the surface of the cured film B below, respectively. The absolute value of the surface free energy difference is 30% or less of the surface free energy of the cured film A below.
a thermosetting photosensitive composition;
Cured film A: When a coating film of the thermosetting photosensitive composition is formed on a flat support to a thickness of 150% of the average thickness of the thermosetting photosensitive layer, and then heated at 250° C. for 120 minutes. A cured film of the thermosetting photosensitive composition obtained in;
Cured film B: When a coating film of the thermosetting photosensitive composition is formed on a flat support in a thickness of 50% of the average thickness of the thermosetting photosensitive layer, and then heated at 250° C. for 120 minutes. A cured film of the thermosetting photosensitive composition obtained in;

In the above formula (1), γ _s ^d is the dispersion component of the surface free energy of the cured film, γ _sh is the polar component of the surface free energy of the cured film, and γ _L ^d is the dispersion of ^the surface free energy of water or diiodomethane. γ _L ^h is the polar component of the surface free energy of water or diiodomethane, γ _L ^total is the surface free energy of water or diiodomethane, and cos θ is the contact angle of water or diiodomethane;
Here, the surface free energy is represented by the ^sum of the dispersive component and the polar component ^. The dispersive component of the surface free energy of diiodomethane is 48.1 mJ/m ² and the polar component of the surface free energy of diiodomethane is 1.3 mJ/m ² .
<2> The thermosetting photosensitive composition according to <1>, wherein the content of the surfactant is more than 0.1% by mass relative to the total mass of the composition.
<3> The thermosetting photosensitive composition according to <1>, wherein the content of the surfactant is less than 0.005% by mass relative to the total mass of the composition.
<4> The thermosetting photosensitive composition according to any one of <1> to <3>, wherein the surfactant contains a fluorine atom- and silicon atom-free surfactant.
<5> Any one of <1> to <4>, wherein the content of the hydrocarbon surfactant in the composition is 50% by mass or more relative to the total content of the surfactants. A thermosetting photosensitive composition of
<6> The thermosetting photosensitive composition according to any one of <1> to <5>, wherein the resin contains at least one resin selected from the group consisting of polyimides and polyimide precursors.
<7> The thermosetting photosensitive composition according to any one of <1> to <6>, which is used for forming a thermosetting photosensitive layer by a slit coating method.
<8> The thermosetting photosensitive composition according to any one of <1> to <6>, which is used for forming a thermosetting photosensitive layer by spin coating.
<9> The thermosetting photosensitive composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured film obtained by curing the thermosetting photosensitive composition according to any one of <1> to <9>.
<11> A laminate comprising two or more layers of the cured film according to <10> and a metal layer between any of the cured films.
<12> A method for producing a cured film, comprising a film forming step of applying the thermosetting photosensitive composition according to any one of <1> to <9> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, comprising an exposure step of exposing the film and a development step of developing the film.
<14> The method for producing a cured film according to <12> or <13>, comprising a heating step of heating the film at 50 to 450°C.
<15> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.

According to the present invention, even if a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film, defects occur in the other layer is suppressed thermosetting photosensitive composition, a cured film obtained by curing the thermosetting photosensitive composition, a laminate containing the cured film, a method for producing the cured film, and the cured film or the A semiconductor device is provided that includes a laminate.

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

(Thermosetting photosensitive composition)
The thermosetting photosensitive composition of the present invention is a thermosetting photosensitive composition used for forming a thermosetting photosensitive layer, and is a group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors. At least one resin (hereinafter also referred to as "specific resin") selected from The absolute value of the difference between the surface free energy of the cured film A below and the surface free energy of the cured film B below calculated using the formula (1) from the contact angle and the contact angle of diiodomethane is the surface free energy of the cured film A below. 30% or less.
Cured film A: When a coating film of the thermosetting photosensitive composition is formed on a flat support to a thickness of 150% of the average thickness of the thermosetting photosensitive layer, and then heated at 250° C. for 120 minutes. Cured film of the thermosetting photosensitive composition obtained in Cured film B: The coating film of the thermosetting photosensitive composition is flat with a thickness of 50% of the average thickness of the thermosetting photosensitive layer A cured film of the thermosetting photosensitive composition obtained by heating at 250° C. for 120 minutes after forming on a support.

As a first aspect, the thermosetting photosensitive composition of the present invention preferably contains a specific resin, a photopolymerization initiator as the photosensitive agent, a surfactant, and a solvent.
The thermosetting photosensitive composition of the present invention in the first aspect preferably further contains a radical cross-linking agent.
Moreover, in the first aspect, an aspect further including a thermal cross-linking agent is preferred, and an aspect further including a thermal cross-linking agent and a thermal acid generator is more preferred.
As a second aspect, the thermosetting photosensitive composition of the present invention preferably contains a specific resin, a photoacid generator as the photosensitive agent, a surfactant, and a solvent.
It is preferable that the thermosetting photosensitive composition of the present invention in the second aspect further contains a thermal crosslinking agent.
The thermosetting photosensitive composition of the present invention may be a negative thermosetting photosensitive composition or a positive thermosetting photosensitive composition.
A negative thermosetting photosensitive composition is a composition from which the non-exposed areas are removed by development when subjected to development after exposure.
A positive thermosetting photosensitive composition is a composition from which an exposed portion is removed by development when subjected to development after exposure.

According to the thermosetting photosensitive composition of the present invention, even if a cured film is produced by applying it to an uneven substrate, and another layer is further formed on the obtained cured film Also, the occurrence of defects in other layers is suppressed.
Although the mechanism by which the above effects are obtained is unknown, it is presumed as follows.

The thermosetting photosensitive composition is applied to a substrate or the like, and then dried as necessary to form a thermosetting photosensitive layer, and is used for the purpose of obtaining a cured film by heating or the like. .
Also, if necessary, patterning may be performed by exposure and development, for example, before heating.
As a result of intensive studies, the present inventors formed a thermosetting photosensitive layer on a non-uniform substrate such as having a step, and after obtaining a cured film, further formed another layer on the cured film. It has been found that defects may occur in other layers when the layer is formed.
Since a solvent exists in the thermosetting photosensitive layer before drying, at least part of the components in the thermosetting photosensitive composition (for example, components that easily migrate in the composition film, such as surfactants) migrates to the surface of the composition film.
Here, a non-uniform base material (for example, a base material having a step on the surface, a base material having a slope on the surface, etc., a base material having an uneven physical shape on the surface of the base material, or When a thermosetting photosensitive layer is formed on a base material with uneven surface chemical properties, such as a base material that is difficult to mix with the composition only on the part, the thickness of the thermosetting photosensitive layer is uniform. may not be. For example, in a substrate having a step on the surface, the thermosetting photosensitive layer is thin in the convex portions of the substrate surface, and thick in the concave portions of the substrate surface.
Further, for example, in a base material having a slope on the surface, the thermosetting photosensitive layer is thick in the portion where the slope is low and the thermosetting photosensitive layer is thick in the portion where the slope is high.
Furthermore, for example, in the case of a substrate where only a part of the surface is difficult to be compatible with the composition, the thermosetting photosensitive layer is thin because the composition easily spreads in the part that is compatible with the composition, and the composition is not compatible in the part that is difficult to be compatible with the composition. is difficult to spread, the thermosetting photosensitive layer becomes thick.
Since components such as the above-mentioned surfactants migrate from the inside of the thermosetting photosensitive layer, there are many of the above components that migrate to the surface in areas where the thermosetting photosensitive layer is thick, and in areas where the thermosetting photosensitive layer is thin, the surface It is thought that the above-mentioned components that migrate to the Such a thermosetting photosensitive composition having different component distributions depending on the position on the surface is cured to form a cured film, and when another layer is formed on the cured film, depending on the position on the surface of the cured film It is considered that defects occur in the other layers due to differences in coatability and the like when forming the other layers.
The composition of the present invention is a composition that provides a cured film with a small difference in surface free energy with respect to changes in film thickness. Therefore, it is presumed that the occurrence of defects in the other layers is suppressed.
Suppression of the occurrence of the above defects is considered to be particularly remarkable, for example, when the thermosetting photosensitive layer is formed by a method such as a slit coating method that takes a long time to dry after coating.

Here, Patent Literature 1 does not describe or suggest a thermosetting photosensitive composition having a specific difference in surface free energy.
The properties and components contained in the thermosetting photosensitive composition of the present invention are described in detail below.

上記式（１）中、γ_ｓ ^ｄは硬化膜の表面自由エネルギーの分散成分を、γ_ｓ ^ｈは硬化膜の表面自由エネルギーの極性成分を、γ_L ^ｄは水又はジヨードメタンの表面自由エネルギーの分散成分を、γ_L ^ｈは水又はジヨードメタンの表面自由エネルギーの極性成分を、γ_L ^ｔоｔaｌは水又はジヨードメタンの表面自由エネルギーを、ｃоｓθは水又はジヨードメタンの接触角を、それぞれ表す；
ここで、表面自由エネルギーは分散成分と極性成分の和で表され、水の表面自由エネルギーの分散成分は２１．７ｍＪ／ｍ^２、水の表面自由エネルギーの極性成分は５０．８ｍＪ／ｍ^２、ジヨードメタンの表面自由エネルギーの分散成分は４８．１ｍＪ／ｍ^２、ジヨードメタンの表面自由エネルギーの極性成分は１．３ｍＪ／ｍ^２とする。
硬化膜の表面自由エネルギーは、分散成分γ_ｓ ^ｄとγ_ｓ ^ｈの和として求められ、具体的には、下記式（Ｒ１）及び式（Ｒ２）で表される連立方程式を解くことにより求められる。

ここで、θ１は水の接触角であり、θ２はジヨードメタンの接触角である。<Surface free energy>
The thermosetting photosensitive composition of the present invention is a cured film calculated using the formula (1) from the contact angle of water and the contact angle of diiodomethane with respect to the surface of the cured film A and the surface of the cured film B. The absolute value of the difference between the surface free energy of A and the surface free energy of the cured film B is 30% or less of the surface free energy of the cured film A.
In the present invention, the surface free energy is a value calculated using the formula (1) from the contact angle of water and the contact angle of diiodomethane.
Specifically, the surface free energy is obtained by contacting the cured film A or cured film B with 1 μl of water and diiodomethane, respectively, and measuring the respective contact angles. It is the required energy. For example, it can be calculated using the function integration analysis software FAMAS (manufactured by Kyowa Interface Science Co., Ltd.).

In the above formula (1), γ _s ^d is the dispersion component of the surface free energy of the cured film, γ _sh is the polar component of the surface free energy of the cured film, and γ _L ^d is the dispersion of ^the surface free energy of water or diiodomethane. γ _L ^h is the polar component of the surface free energy of water or diiodomethane, γ _L ^total is the surface free energy of water or diiodomethane, and cos θ is the contact angle of water or diiodomethane;
Here, the surface free energy is represented by the ^sum of the dispersive component and the polar component ^. The dispersive component of the surface free energy of diiodomethane is 48.1 mJ/m ² and the polar component of the surface free energy of diiodomethane is 1.3 mJ/m ² .
The surface free energy of the cured film is obtained as the sum of the dispersion components γ _s ^d and _γ ^sh , and specifically, it is obtained by solving the simultaneous equations represented by the following formulas (R1) and (R2). .

Here, θ1 is the contact angle of water, and θ2 is the contact angle of diiodomethane.

上記厚さＴ１、Ｔ２、Ｔｉ等の熱硬化性感光層の厚さは、例えばエリプソメーター（Ｆｏｏｔｈｉｌｌ社製ＫＴ－２２）を用いて測定される。The average thickness of the thermosetting photosensitive layer is the average thickness of the entire surface of the thermosetting photosensitive layer applied to the substrate. When the area is S1, the area where the thermosetting photosensitive layer having a thickness of T2 is formed is S2, and the sum of the areas S1 and S2 is the total area of the thermosetting photosensitive layer, it is calculated by the following formula. be.
Average thickness = T1 x S1/(S1 + S2) + T2 x S2/(S1 + S2)
Similarly, the areas in which n types of thermosetting photosensitive layers having a thickness of Ti are formed are respectively Si (i is an integer from 1 to n, S1 + S2 + ... + Sn is the total area of the thermosetting photosensitive layer ), the average thickness is calculated by the following formula.

The thicknesses of the thermosetting photosensitive layer such as the thicknesses T1, T2 and Ti are measured using, for example, an ellipsometer (KT-22 manufactured by Foothill).

The surface free energy of the cured film A is preferably from 10 to 50 mJ/m ² , more preferably from 15 to 40 mJ/m ² , even more preferably from 20 to 35 mJ/m ² .
The surface free energy of the cured film B is preferably 10 to 50 mJ/m ² , more preferably 15 to 40 mJ/m ² and even more preferably 20 to 35 mJ/m ² .

The absolute value of the difference between the surface free energy of the cured film A and the surface free energy of the cured film B is 30% or less, more preferably 20% or less, of the surface free energy of the cured film A. % or less. The lower limit is not particularly limited, and may be 0% or more.

The ratio of the absolute value of the difference between the surface free energy of the cured film A and the surface free energy of the cured film B to the surface free energy of the cured film A is a value determined by the composition of the thermosetting photosensitive composition. and is considered to be determined by, for example, the amount of surfactant in the thermosetting photosensitive composition, the type of surfactant, and the like.

The method for producing the coating film in the cured film A and the cured film B is not particularly limited, but by the same method as the method for producing the coating film in the formation of the thermosetting photosensitive layer using the thermosetting photosensitive composition of the present invention. is preferably made.
For example, when the thermosetting photosensitive layer is produced by the slit coating method, it is preferable that the coated films in the cured film A and the cured film B are also produced by the slit coating method.

Further, in the thermosetting photosensitive composition of the present invention, the absolute value of the difference between the surface free energy of the cured film C described below and the surface free energy of the cured film D described below is 30% or less of the surface free energy of the cured film C described below. preferably 20% or less, and even more preferably 10% or less. The lower limit is not particularly limited, and may be 0% or more.
Cured film C: The above thermosetting photosensitive composition obtained by forming a coating film of the above thermosetting photosensitive composition to a thickness of 45 μm on a flat support and heating at 250° C. for 120 minutes. Cured film Cured film D: The thermosetting photosensitive composition obtained by forming a coating film of the thermosetting photosensitive composition with a thickness of 15 μm on a flat support and then heating at 250 ° C. for 120 minutes. Cured film of the adhesive composition

<Specific resin>
The thermosetting photosensitive composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors.
The specific resin preferably contains at least one resin selected from the group consisting of polyimides and polyimide precursors.
Furthermore, it is preferable that the resin contains a polymerizable group and the photosensitive resin composition contains a polymerizable compound. By adopting such a structure, a three-dimensional network is formed in the exposed area, forming a strong crosslinked film, making the photosensitive resin composition layer (resin layer) less likely to be damaged by the surface activation treatment. Thus, the adhesion is more effectively improved. It is particularly effective in adhesion to the upper layer. Furthermore, the polyimide and polybenzoxazole contained in the resin layer in the laminate of the present invention preferably contain a partial structure represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO ₂ — or —NHCO—, or a group consisting of a combination of two or more of the above. With such a configuration, the resin layer has a flexible structure, and the occurrence of peeling can be suppressed more effectively. Ar is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO ₂ - . The aliphatic hydrocarbon group here is preferably an alkylene group.

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

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

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

R ¹¹¹ is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof It is preferably a diamine containing, more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of groups containing aromatic groups include:

式中、Ａは、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ_２－、及び－ＮＨＣＯ－、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、及び、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基であることが更に好ましい。

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

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diamino diphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl ) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl) ) sulfone, 4,4′-diaminoparaterphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy ) phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3′- dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-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'-hexafluorotolyzine and 4,4'-diaminoquaterphenyl can be used.

Diamines (DA-1) to (DA-18) shown below are also preferred.

Diamines having at least two or more alkylene glycol units in the main chain are also preferred examples. Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule are more preferred, and diamines containing no aromatic ring are even more preferred. Specific examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (Trade names above, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)) Propan-2-yl)oxy)propan-2-amine and the like, but are not limited thereto.
The structures of Jeffamine® KH-511, ED-600, ED-900, ED-2003, EDR-148 and EDR-176 are shown below.

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

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

式（５１）中、Ｒ^５０～Ｒ^５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ^５０～Ｒ^５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基であり、＊はそれぞれ独立に、式（２）中の窒素原子との結合部位を表す。
Ｒ^５０～Ｒ^５７の１価の有機基としては、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。

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

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
The monovalent organic groups represented by R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group.
Diamine compounds that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′- bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used.

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

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

Formula (6)

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

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

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

In addition, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) are also preferred examples.

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

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy It preferably contains a group, and more preferably contains a polyalkyleneoxy group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, more preferably both contain a polymerizable group. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, an amino groups. A group having an ethylenically unsaturated bond is preferable as the radically polymerizable group possessed by the polyimide precursor or the like.
Examples of groups having an ethylenically unsaturated bond include vinyl groups, (meth)allyl groups, groups represented by the following formula (III), and the like.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, more preferably a hydrogen atom or a methyl group.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ — or a polyoxyalkylene group having 4 to 30 carbon atoms.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group. An alkylene group such as -CH2CH(OH)CH2- is mentioned, and an ethylene group, a propylene group, a trimethylene group, and -CH2CH(OH)CH2- are more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

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

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms in the alkyl group is preferably 1-30. Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, 2-(2-(2 -ethoxyethoxy)ethoxy)ethoxy)ethoxy group, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy group ) ethoxy groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. is mentioned. Among them, a cyclohexyl group is most preferable from the viewpoint of compatibility with high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group, which will be described later, is preferable.
Specific examples of aromatic groups include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene ring. ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring , indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring or phenazine ring. A benzene ring is most preferred.

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

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

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

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

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.

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

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

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, still more preferably 22,000 to 25,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The polyimide precursor preferably has a molecular weight distribution of 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. Although the upper limit of the polyimide precursor molecular weight dispersity is not particularly defined, for example, it is preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, and even more preferably 3.2 or less. It is preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.
On the other hand, from the viewpoint of developability, the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. is. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
From the viewpoint of developability, the molecular weight distribution of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and even more preferably 2.2 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In the present specification, the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.

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

- Fluorine atom -
From the viewpoint of film strength of the resulting cured film, the polyimide preferably has a fluorine atom.
A fluorine atom is preferably included in, for example, R ¹³² in a repeating unit represented by formula (4) described later or R ¹³¹ in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R ¹³² in the repeating unit represented by 4) or R ¹³¹ in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of polyimide is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.

-Silicon atom-
From the viewpoint of film strength of the resulting cured film, the polyimide preferably has a silicon atom.
A silicon atom, for example, is preferably contained in R ¹³¹ in a repeating unit represented by formula (4) described later, and R ¹³¹ in a repeating unit represented by formula (4) described later is an organically modified (poly ) is more preferably contained as a siloxane structure.
The silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of polyimide is preferably 0.01 to 5 mol/g, more preferably 0.05 to 1 mol/g.

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

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, more preferably a hydrogen atom or a methyl group.

In formula (III), R ²⁰¹ 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)oxyalkylene group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.
In addition, a (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

式（Ｒ１）～（Ｒ３）中、Ｌは単結合、又は、炭素数２～１２のアルキレン基、炭素数２～３０の（ポリ）オキシアルキレン基若しくはこれらを２以上結合した基を表し、Ｘは酸素原子又は硫黄原子を表し、＊は他の構造との結合部位を表し、●は式（ＩＩＩ）中のＲ^２０１が結合する酸素原子との結合部位を表す。
式（Ｒ１）～（Ｒ３）中、Ｌにおける炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）オキシアルキレン基の好ましい態様は、上述のＲ^２０１における、炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）オキシアルキレン基の好ましい態様と同様である。
式（Ｒ１）中、Ｘは酸素原子であることが好ましい。
式（Ｒ１）～（Ｒ３）中、＊は式（ＩＩＩ）中の＊と同義であり、好ましい態様も同様である。
式（Ｒ１）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物（例えば、２－イソシアナトエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ２）で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物（例えば、２－ヒドロキシエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ３）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物（例えば、グリシジルメタクリレート等）とを反応することにより得られる。Among these, R ²⁰¹ is preferably a group represented by any one of formulas (R1) to (R3) below, 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)oxyalkylene group having 2 to 30 carbon atoms, or a group in which two or more of these are combined, and X represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ● represents a bonding site with the oxygen atom to which R ²⁰¹ in formula (III) bonds.
In formulas (R1) to (R3), a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)oxyalkylene group having 2 to 30 carbon atoms in L is the above-mentioned R ²⁰¹ having 2 to 2 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)oxyalkylene 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 (III), and preferred embodiments are also the same.
The structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.

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

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

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

- Acid value -
When polyimide is subjected to alkali development, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable.
Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, and 3 to 30 mgKOH. /g is more preferred, and 5 to 20 mgKOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
As the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, the values listed in the Chemical Society of Japan, Revised 5th Edition, Basics of Chemistry, may be referred to.
Also, when the acid group is a polyvalent acid such as phosphoric acid, the 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, more preferably a phenolic hydroxy group.

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

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

式（４－１）中、Ｒ¹³³は重合性基であり、他の基は式（４）と同義である。
式（４－２）

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

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

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

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

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

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

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

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

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

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

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

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

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

-Imidation rate (ring closure rate)-
The imidization rate of polyimide (also referred to as "ring closure rate") is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulation properties, etc. of the resulting cured film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured, for example, by the method described below.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C. for 1 hour, the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula.
Imidation rate (%) = (peak intensity P1/peak intensity P2) x 100

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

For polyimide, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid A method of reacting a diamine compound with a diamine compound, a method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a monoactive ester compound, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent with a tetracarboxylic dianhydride and an alcohol to obtain a diester, then acid chloride the remaining dicarboxylic acid, diamine (a part of which is a monoamine Substitution with a terminal blocking agent) is used to obtain a polyimide precursor, which is completely imidized using a known imidization reaction method, or imide in the middle Synthesis using a method of stopping the polymerization reaction and partially introducing an imide structure, or a method of partially introducing an imide structure by blending a completely imidized polymer with its polyimide precursor. can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when two or more types of polyimide are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is within the above range.
On the other hand, from the viewpoint of chemical resistance, the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000.

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

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

In formula (3), R ¹²³ and R ¹²⁴ each have the same meaning as R ¹¹³ in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, thoria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

（式中、Ｚは炭素数１～６の炭化水素基であり、ｎは１～６の整数である。）

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

As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferable, and the following dicarboxylic acids consisting of only a group having an aromatic group and two —COOH are more preferable.

式中、Ａは－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、及び、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。

wherein A is -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - represents a divalent group selected from the group consisting of

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (2), and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. -diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino- 4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, 4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination.

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

式中、Ｘ_１は、－Ｏ－、－Ｓ－、－Ｃ（ＣＦ_３）_２－、－ＣＨ_２－、－ＳＯ_２－、－ＮＨＣＯ－を表す。

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-.

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc). _R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. _R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

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

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

In the above formula (A-s), the ortho position of the phenolic hydroxyl group, that is, having a substituent also at R ₃ is thought to make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and cured at a low temperature. It is particularly preferable in that the effect of increasing the cyclization rate is further enhanced.

Further, in the above formula (A-s), when R ₂ is an alkyl group and R ₃ is an alkyl group, high transparency to the i-line and high cyclization rate when cured at a low temperature are said to be obtained. It is preferable because the effect can be maintained.

Further, in formula (As) above, it is more preferred that R ₁ is alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene for R ₁ include -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 _{2CH 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 _{( CH2CH2CH2CH2CH3 ) - , -C ( CH3 ) ( CH2CH2CH2CH2CH3 ) - , -CH} ( _{CH2CH2CH2CH2CH2CH3 )} -, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, 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-line and high cyclization rate when cured at low temperature. It is more preferable in that it can be obtained.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506. , the contents of which are incorporated herein.

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

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

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

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

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

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor, for example, when used in the composition described later, is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further Preferably it is 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.

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

式（Ｘ－１）中、Ｒ^１３５及びＲ^１３６の少なくとも一方は、重合性基であり、重合性基でない場合は有機基であり、他の基は式（Ｘ）と同義である。
式（Ｘ－２）

式（Ｘ－２）中、Ｒ^１３７は重合性基であり、他は置換基であり、他の基は式（Ｘ）と同義である。[Polybenzoxazole]
Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group.

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
When it has a polymerizable group, the polymerizable group may be located on at least one of R ¹³³ and R ¹³⁴ , and polybenzoxazole as shown in the following formula (X-1) or formula (X-2) may be located at the end of the
Formula (X-1)

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (X).
Formula (X-2)

In formula (X-2), R ¹³⁷ is a polymerizable group, the others are substituents, and the other groups are the same as in formula (X).

The polymerizable group is synonymous with the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like.

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

R ¹³⁴ represents a tetravalent organic group. Tetravalent organic groups include examples of R ¹²² in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of ^R122 .
For example, four bonds of a tetravalent organic group exemplified as R ¹²² combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, it forms the structure below.

Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when the film is oxazolized by heating can be reduced, and the occurrence of warpage can be more effectively suppressed.

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

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

The weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.

[Method for producing polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction.
One type of organic solvent may be used, or two or more types may be used.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
Polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promoting the cyclization reaction by acting a catalyst), or directly , polyimide may be synthesized.

-Terminal blocking agent-
In the production method of polyimide precursors, etc., in order to further improve the storage stability, terminal blockers such as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds are used to block the ends of polyimide precursors. Sealing is preferred. Monoalcohols, phenols, thiols, thiophenols, and monoamines are more preferably used as terminal blocking agents.
Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, t-butyl alcohol, adamantane alcohol and other tertiary alcohols, and the like. Preferred phenolic compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and the like.
Preferred compounds of monoamines 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-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-amino benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. be done. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
Moreover, when blocking the amino group at the terminal of the resin, it is possible to block with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and the like. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.

-Solid precipitation-
A step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water and then dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor or the like is soluble, thereby allowing solid deposition.
Thereafter, the polyimide precursor or the like is dried to obtain a powdery polyimide precursor or the like.

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

<Photosensitizer>
A thermosetting photosensitive composition contains a photosensitizer.
As for the photosensitive agent, when the thermosetting photosensitive layer is exposed to light, a chemical change such as generation of radicals or acid occurs. Although it is not particularly limited as long as it is a compound having an effect of changing the solubility of , examples thereof include photopolymerization initiators and photoacid generators.

[Photopolymerization initiator]
Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.

- Photoradical polymerization initiator -
The thermosetting photosensitive composition of the present invention preferably contains a photoradical polymerization initiator.
For example, by containing a radical photopolymerization initiator and a radical cross-linking agent described later, radical polymerization proceeds and the exposed portion of the thermosetting photosensitive layer becomes insoluble in the developer, thereby forming a negative pattern. can do.
The radical photopolymerization initiator is not particularly limited, and can be appropriately selected from known compounds, for example. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.

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

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

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

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

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

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

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

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

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

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

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

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the thermosetting photosensitive composition of the present invention, it is particularly preferable to use an oxime compound (an oxime radical photopolymerization initiator) as the photoradical polymerization initiator. An oxime compound that is a photoradical polymerization initiator has a linking group represented by >C=N--O--C(=O)- in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP-A-2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

Oxime compounds having the structures below can also be used.

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

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

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

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

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

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

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

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

The content of the photoradical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. Yes, more preferably 0.5 to 15% by mass, still more preferably 1.0 to 10% by mass. Only one type of radical photopolymerization initiator may be contained, or two or more types may be contained. When two or more radical photopolymerization initiators are contained, the total is preferably within the above range.

-Thermal radical polymerization initiator-
The thermosetting photosensitive composition of the present invention may further contain a thermal radical polymerization initiator.
A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the radical polymerization reaction proceeds further during heating, so that the crosslink density can be further improved in some cases.

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

When a thermal radical polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 30% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. 20% by mass, more preferably 5 to 15% by mass. One type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.

- Photoacid generator -
The thermosetting photosensitive composition of the present invention preferably contains a photoacid generator.
By containing a photoacid generator, for example, an acid is generated in the exposed area of the thermosetting photosensitive layer, the solubility of the exposed area in the developer (eg, alkaline aqueous solution) increases, and the exposed area develops. A positive relief pattern can be obtained which is removed by liquid.
Further, when the thermosetting photosensitive composition contains a photoacid generator and a thermal cross-linking agent described later, for example, the acid generated in the exposed area accelerates the cross-linking reaction of the thermal cross-linking agent, can be made more difficult to remove by the developer than the non-exposed portion. According to such an aspect, a negative relief pattern can be obtained.

Examples of photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.

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

In the present invention, both 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group are preferably used as quinonediazide. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength. Further, a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinone diazidesulfonyl group and a 5-naphthoquinone diazidesulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazidesulfonyl ester compound and a 5-naphthoquinone diazidesulfonyl ester compound may be contained. may contain.

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

When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20%, based on the total solid content of the thermosetting photosensitive composition of the present invention. % by mass, more preferably 5 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably within the above range.

-Thermal acid generator-
The thermosetting photosensitive composition of the present invention may contain a thermal acid generator.
The thermal acid generator is not particularly limited as long as it is a compound that generates an acid by heat. Examples include onium salts such as sulfonium salts, ammonium salts, and phosphonium salts; Examples include ester compounds such as ester compounds.

Examples of the acid generated from the thermal acid generator by heating include sulfonic acid, phosphoric acid, and carboxylic acid, with sulfonic acid being preferred, and aromatic sulfonic acid being more preferred.
The pKa of the acid generated from the thermal acid generator is preferably -15 to 3, more preferably -10 to 0.

The acid generation temperature of the thermal acid generator is preferably 40 to 300°C, more preferably 80 to 260°C, even more preferably 120 to 220°C, and 120 to 200°C. is particularly preferred, and 140°C to 180°C is most preferred.
The acid generation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated up to 500° C. in a pressure-resistant capsule at 5° C./min.
Equipment used for measuring the acid generation temperature includes Q2000 (manufactured by TA Instruments).
Moreover, the acid generation temperature of the thermal acid generator is preferably lower than the boiling point of the solvent contained in the thermosetting photosensitive composition.

Commercially available suitable thermal acid generators include Sanshin Chemical Industry's San-Aid SI series, Sun-Apro's CPI series, and King's K-PURE TAG series.
In addition, JP-A-2003-277353, JP-A-2-001470, JP-A-2-255646, JP-A-3-011044, JP-A-2003-183313, JP-A-2003-277352, JP-A-58-037003 No. 58-198532, and other publications such as JP-A-58-198532 can also be used.

The content of the thermal acid generator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. It is preferably 0.5 to 15% by mass, particularly preferably 1.0 to 10% by mass.
One type of thermal acid generator may be contained, or two or more types may be contained. When two or more thermal acid generators are contained, the total is preferably within the above range.

<Surfactant>
The thermosetting photosensitive composition of the invention contains a surfactant.
Examples of surfactants include silicone surfactants, hydrocarbon surfactants, nonionic surfactants such as fluorine surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Various types of surfactants can be used, and nonionic surfactants are preferred from the viewpoint of the insulating properties of the cured film.

In the thermosetting photosensitive composition of the present invention, the surfactant content is preferably more than 0.1% by mass relative to the total mass of the composition.
In the above aspect, the thermosetting photosensitive composition of the present invention is selected from the group consisting of a hydrocarbon surfactant described later, a surfactant having a fluorine atom described later, and a surfactant having a silicon atom described later. At least one selected surfactant can be included.
When two or more surfactants are contained, the total is preferably within the above range.
The lower limit of the content is more preferably 0.101% by mass or more, preferably 0.105% by mass or more.
The upper limit of the content is preferably 5% by mass or less, more preferably 1% by mass or less.
By adopting an aspect containing a large amount of such a surfactant, for example, even in a portion where the thermosetting photosensitive layer is thin on an uneven substrate, the surface of the thermosetting photosensitive layer can be improved by a large amount of surfactant. are considered to be covered. Therefore, the difference in the amount of surfactant present on the surface of the thermosetting photosensitive layer between the thick portion and the thin portion of the thermosetting photosensitive layer becomes small, and the surface free energy of each of the cured film A and the cured film B It is thought that the difference between As a result, even when a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film, the occurrence of defects in the other layer is suppressed. considered to be easy.

Moreover, in the thermosetting photosensitive composition of the present invention, the content of the surfactant is preferably less than 0.005% by mass with respect to the total mass of the composition.
In the above aspect, the thermosetting photosensitive composition of the present invention is selected from the group consisting of a hydrocarbon surfactant described later, a surfactant having a fluorine atom described later, and a surfactant having a silicon atom described later. At least one selected surfactant can be included.
When two or more surfactants are contained, the total is preferably within the above range.
The lower limit of the content is more preferably 0.0001% by mass or more, and preferably 0.0005% by mass or more.
The upper limit of the content is preferably 0.0045% by mass or less, more preferably 0.0042% by mass or less.
By adopting a mode in which the content of such a surfactant is small, for example, even if the thermosetting photosensitive layer is thin or thick in a non-uniform substrate, the thermosetting photosensitive layer Less surfactant is believed to migrate to the surface of the layer. Therefore, the difference in the amount of surfactant present on the surface of the thermosetting photosensitive layer between the thick portion and the thin portion of the thermosetting photosensitive layer becomes small, and the surface free energy of each of the cured film A and the cured film B It is thought that the difference between As a result, even when a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film, the occurrence of defects in the other layer is suppressed. considered to be easy.

The thermosetting photosensitive composition of the present invention preferably contains a fluorine atom- and silicon atom-free surfactant. Examples of surfactants having no fluorine atom and silicon atom include hydrocarbon-based surfactants described later.
It is considered that the surface free energy of the cured film tends to decrease when the surfactant having fluorine atoms or silicon atoms migrates to the surface of the thermosetting photosensitive layer. Therefore, by including a surfactant that does not have a fluorine atom and a silicon atom as a surfactant, the amount of surfactant present on the surface of the thermosetting photosensitive layer in the thick and thin portions of the thermosetting photosensitive layer Even if there is a difference in the surface free energies of the cured film A and the cured film B, it is considered that the difference in surface free energy between them becomes small. As a result, even when a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film, the occurrence of defects in the other layer is suppressed. considered to be easy.

In the thermosetting photosensitive composition of the present invention, the content of the hydrocarbon surfactant in the composition is preferably 50% by mass or more relative to the total content of the above surfactants.
In the above aspect, the thermosetting photosensitive composition of the present invention includes at least one surfactant selected from the group consisting of a fluorine atom-containing surfactant described later and a silicon atom-containing surfactant described later. It may further contain an agent.
The content is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit is not particularly limited, and may be 100% by mass.
When two or more kinds of hydrocarbon surfactants are contained, the total is preferably within the above range.
The details of the hydrocarbon surfactant will be described later.
Even if the hydrocarbon surfactant migrates to the surface of the thermosetting photosensitive layer, it is considered that the surface free energy of the cured film is unlikely to decrease. Therefore, when the content of the hydrocarbon-based surfactant in the composition is 50% by mass or more with respect to the total content of the above surfactants, the portions where the thermosetting photosensitive layer is thick and the portions where the thermosetting photosensitive layer is thin Even if there is a difference in the amount of surfactant present on the surface of the thermosetting photosensitive layer, the difference in surface free energy between cured film A and cured film B is considered to be small. As a result, even when a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film, the occurrence of defects in the other layer is suppressed. considered to be easy.

[Hydrocarbon Surfactant]
The hydrocarbon-based surfactant may be a surfactant having a hydrocarbon group as the hydrophobic part, and the acetylene-based surfactants, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether described later. Polyoxyethylene alkyl ethers such as, or esters such as phosphate esters thereof, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, etc. Polyoxyethylene alkyl esters, sorbitan alkyl esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, glycerol monostearate, glycerol monooleate Nonionic surfactants such as monoglyceride alkyl esters such as ate, polynuclear phenol ethoxylates;
Alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonates such as sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, sodium octylnaphthalenesulfonate, alkylsulfuric acids such as sodium laurylsulfate Anionic surfactants such as salts, alkylsulfonates such as sodium dodecylsulfonate, sulfosuccinate salts such as sodium dilaurylsulfosuccinate;
Cationic surfactants such as quaternary ammonium salt-type alkyl cations;
Examples include amphoteric surfactants such as alkylbetaines such as laurylbetaine and stearylbetaine, but are not limited thereto.

-Acetylene surfactant-
The number of acetylene groups in the molecule in the acetylenic surfactant is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1 to 2. preferable.

The molecular weight of the acetylenic surfactant is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, even more preferably 1,000 or less. Although there is no particular lower limit, it is preferably 200 or more.

式中、Ｒ^９１及びＲ^９２は、それぞれ独立に、炭素数３～１５のアルキル基、炭素数６～１５の芳香族炭化水素基、又は、炭素数４～１５の芳香族複素環基である。芳香族複素環基の炭素数は、１～１２が好ましく、２～６がより好ましく、２～４が更に好ましい。
芳香族複素環は５員環又は６員環が好ましい。芳香族複素環が含むヘテロ原子は窒素原子、酸素原子、又は硫黄原子が好ましい。
Ｒ^９１及びＲ^９２は、それぞれ独立に、置換基を有していてもよく、置換基としては下記置換基Ｔが挙げられる。<<Compound Represented by Formula (9)>>
The acetylenic surfactant is preferably a compound represented by the following formula (9).

In the formula, R ⁹¹ and R ⁹² are each independently an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. . The number of carbon atoms in the aromatic heterocyclic group is preferably 1-12, more preferably 2-6, even more preferably 2-4.
The aromatic heterocycle is preferably a 5- or 6-membered ring. A heteroatom contained in the aromatic heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
Each of R ⁹¹ and R ⁹² may independently have a substituent, and examples of the substituent include the following substituent T.

The substituent T is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , more preferably 7 to 11), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl groups (preferably 2 to 12 carbon atoms, 2 to 6 are more preferably 2 to 3), hydroxy group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms), thiol group, carboxy group, aryl group (carbon Number 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), alkoxyl group (C1 to 12 is preferable, 1 to 6 is more preferable, 1 to 3 is still more preferable), aryloxy Group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10 carbon atoms), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3) , an acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), an aryloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, more preferably 7 to 11 preferred), aryloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 11 carbon atoms), carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 3 are more preferred), sulfamoyl groups (preferably 0 to 12 carbon atoms, more preferably 0 to 6, more preferably 0 to 3), sulfo groups, alkylsulfonyl groups (preferably 1 to 12 carbon atoms, 1 to 6 is more preferred, and 1 to 3 are more preferred), arylsulfonyl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), heterocyclic groups (having 1 to 12 carbon atoms preferably 1 to 8, more preferably 2 to 5, preferably containing a 5- or 6-membered ring), (meth)acryloyl group, (meth)acryloyloxy group, halogen atom (e.g., fluorine atom , chlorine atom, bromine atom, iodine atom), oxo group (=O), imino group (=NR ^N ), alkylidene group (=C(R ^N ) ₂ ) and the like. R ^{3 N} is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, linear or branched. When the substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, a (meth)acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxy group or an amino group, the group may form a salt.

<<Compound Represented by Formula (91)>>
The compound represented by Formula (9) is preferably a compound represented by Formula (91) below.

R ⁹³ to R ⁹⁶ are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, and n10 is an integer of 1 to 6. is an integer, m10 is an integer twice as large as n10, and l9 and l10 are each independently a number of 0 or more and 12 or less.
R ⁹³ to R ⁹⁶ are hydrocarbon groups, and among them, alkyl groups (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), alkenyl groups (having 2 to 12 carbon atoms preferably 2 to 6, more preferably 2 to 3), alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), aryl group (6 to 22 is preferred, 6 to 18 are more preferred, and 6 to 10 are even more preferred), and an arylalkyl group (having preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11) is preferred. . Alkyl groups, alkenyl groups, and alkynyl groups may be linear or cyclic, and may be linear or branched. R ⁹³ to R ⁹⁶ may have a substituent T as long as the effects of the present invention are exhibited. In addition, R ⁹³ to R ⁹⁶ may be bonded to each other or may form a ring through the linking group L described above. When there are a plurality of substituents T, they may be bonded to each other or may be bonded to a hydrocarbon group in the formula with or without a linking group L below to form a ring.
R ⁹³ and R ⁹⁴ are preferably alkyl groups (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms). Among them, a methyl group is preferred.
R ⁹⁵ and R ⁹⁶ are preferably alkyl groups (having preferably 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 3 to 6 carbon atoms). Of these, -(C _n11 R ⁹⁸ _m11 )-R ⁹⁷ is preferred. R ⁹⁵ and R ⁹⁶ are particularly preferably isobutyl groups.
n11 is an integer of 1-6, preferably an integer of 1-3. m11 is twice the number of n11.
R ⁹⁷ and R ⁹⁸ are each independently preferably a hydrogen atom or an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms).
n9 is an integer of 1-6, preferably an integer of 1-3. m9 is an integer twice as large as n9.
n10 is an integer of 1-6, preferably an integer of 1-3. m10 is an integer that is twice n10.
l9 and l10 are each independently a number from 0 to 12. However, l9+l10 is preferably a number from 0 to 12, more preferably a number from 0 to 8, still more preferably a number from 0 to 6, more preferably a number greater than 0 and less than 6, more than 0 A number of 3 or less is even more preferred. Regarding l9 and l10, the compound of formula (91) may be a mixture of compounds with different numbers, in which case the number of l9 and l10, or l9+l10 is a number including decimal places. may

Ｒ^９３、Ｒ^９４、Ｒ^９７～Ｒ^１００は、それぞれ独立に、炭素数１～２４の炭化水素基であり、ｌ１１及びｌ１２は、それぞれ独立に、０以上１２以下の数である。
Ｒ^９３、Ｒ^９４、Ｒ^９７～Ｒ^１００はなかでもアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が更に好ましい）、アルキニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が更に好ましい）であることが好ましい。アルキル基、アルケニル基、アルキニル基は鎖状でも環状でもよく、直鎖でも分岐でもよい。Ｒ^９３、Ｒ^９４、Ｒ^９７～Ｒ^１００は本発明の効果を奏する範囲で置換基Ｔを有していてもよい。また、Ｒ^９３、Ｒ^９４、Ｒ^９７～Ｒ^１００は互いに結合して、又は連結基Ｌを介して環を形成していてもよい。置換基Ｔは、複数あるときは互いに結合して、あるいは連結基Ｌを介して又は介さずに式中の炭化水素基と結合して環を形成していてもよい。
Ｒ^９３、Ｒ^９４、Ｒ^９７～Ｒ^１００は、それぞれ独立に、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が更に好ましい）であることが好ましい。なかでもメチル基が好ましい。
ｌ１１＋ｌ１２は０～１２の数であることが好ましく、０～８の数であることがより好ましく、０～６の数が更に好ましく、０を超え６未満の数が一層好ましく、０を超え５以下の数がより一層好ましく、０を超え４以下の数が更に一層好ましく、０を超え３以下の数であってもよく、０を超え１以下の数であってもよい。なお、ｌ１１、ｌ１２は、式（９２）の化合物がその数において異なる化合物の混合物となる場合があり、そのときはｌ１１及びｌ１２の数、あるいはｌ１１＋ｌ１２が、小数点以下が含まれた数であってもよい。<<Compound Represented by Formula (92)>>
The compound represented by formula (91) is preferably a compound represented by formula (92) below.

R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, l11 and l12 are each independently a number of 0 or more and 12 or less.
Among R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms) and alkenyl groups (preferably 2 to 12 carbon atoms). , more preferably 2 to 6, more preferably 2 to 3), alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), aryl group (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are even more preferred), and arylalkyl groups (having preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11) are preferred. Alkyl groups, alkenyl groups, and alkynyl groups may be chain or cyclic, and may be linear or branched. R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ may have a substituent T as long as the effects of the present invention are exhibited. In addition, R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ may be bonded to each other or may form a ring through the linking group L. When there are a plurality of substituents T, they may be bonded to each other or bonded to the hydrocarbon group in the formula with or without a linking group L to form a ring.
R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are each independently preferably an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms). Among them, a methyl group is preferred.
l11+l12 is preferably a number of 0 to 12, more preferably a number of 0 to 8, more preferably a number of 0 to 6, more preferably a number of more than 0 and less than 6, more than 0 and 5 or less More preferably, the number is more than 0 and 4 or less is even more preferable, it may be more than 0 and 3 or less, or it may be more than 0 and 1 or less. Note that l11 and l12 may be a mixture of compounds of formula (92) that differ in number, in which case the number of l11 and l12, or l11+l12 is a number including decimal places good too.

As acetylenic surfactants, Surfynol 104 series (trade name, Nissin Chemical Industry Co., Ltd.), Acetyrenol E00, E40, E13T, and 60 (all trade names, Kawaken Fine Chemicals ), among which Surfynol 104 series, acetylenol E00, acetylenol E40 and acetylenol E13T are preferred, and acetylenol E40 and acetylenol E13T are more preferred. Surfynol 104 series and acetylenol E00 are surfactants having the same structure.

In addition, commercial products may be used as hydrocarbon surfactants, and commercial products include adekatol LB, LA, OA, TN, TO, UA, LO, SO, SP, PC, adekatol NK, AP, Adekaestol OEG, TL, S, T, Adekasol CO, COA, Adekahope MS, YES, TR, Adekacol TS, CS, PS, EC, Adekamin 4MAC, 4DAC, MT, Adekaanhort PB, AB series (all ) manufactured by ADEKA) and the like, but are not limited to these.

[Surfactant Having Fluorine Atom]
Surfactants having a fluorine atom include, for example, surfactants having a fluorocarbon chain.
Specifically, the PF series of Kitamura Chemical Industry Co., Ltd., the "Megafac (registered trademark)" series of Dainippon Ink Mfg. (registered trademark)" series, "Asahiguard (registered trademark)" series, EF series of Mitsubishi Materials Electronic Chemicals Co., Ltd., and Polyfox series of Omnova Solution Co., Ltd., but are not limited to these. .

[Surfactant Having Silicon Atom]
Examples of surfactants having silicon atoms (also referred to as “silicone-based surfactants”) include surfactants having polysiloxane chains that may be modified.
Specifically, the silicone-based surfactants include the SH series, SD series, and ST series of Toray Dow Corning Silicone Co., Ltd., the "BYK" series of BYK Chemie Japan, and the KP series and KF of Shin-Etsu Silicone Co., Ltd. series, the Disform series of NOF Corporation, and the TSF series of Toshiba Silicone Co., Ltd., but are not limited to these.

[Other surfactants]
The thermosetting photosensitive composition of the present invention may contain other surfactants as surfactants. Other surfactants include, but are not limited to, acrylic/methacrylic resin surfactants such as Polyflow series from Kyoeisha Chemical Co., Ltd., and "Disparon (registered trademark)" series from Kusumoto Kasei Co., Ltd. not a thing

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

Esters such as 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, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are preferred. .

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate and the like.

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

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

Suitable sulfoxides include, for example, dimethyl sulfoxide.

As amides, 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, and the like.

Alcohols such as 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, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.

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

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- 1 solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more solvents A mixed solvent is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coating properties, the content of the solvent is preferably such that the total solid concentration of the thermosetting photosensitive composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, more preferably 20 to 70% by mass, and 40 to 70% by mass. More preferred. The solvent content may be adjusted according to the desired thickness of the coating and the method of application.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The acid value of the radical cross-linking agent having acid groups is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. On the other hand, from the viewpoint of development speed in alkali development, the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. The acid value is measured according to JIS K 0070:1992.

The thermosetting photosensitive composition of the present invention preferably uses a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG200 diacrylate (polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is 200), 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-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct of bisphenol A Diacrylate, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, EO adduct dimetharylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate A methacrylate, a bifunctional acrylate having a urethane bond, and a bifunctional methacrylate having a urethane bond can be used. These can be used in combination of two or more as needed.
In addition, diallyl phthalate, triallyl trimellitate and the like can be mentioned as the di- or higher functional radical cross-linking agent.
A monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the cured film. Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

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

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

<Thermal cross-linking agent>
The thermosetting photosensitive composition of the present invention preferably contains a thermal cross-linking agent.
The thermal cross-linking agent is particularly limited as long as it is a compound having a plurality of groups in the molecule that promote the reaction to form a covalent bond with other compounds or reaction products thereof in the composition by the action of acid. However, compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups are preferred, and at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to the nitrogen atom. A compound having a structure is more preferred.
As a thermal cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. A compound having a structure represented by The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
As the above amino group-containing compound, a thermal cross-linking agent using melamine is a melamine-based cross-linking agent, a thermal cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and a thermal cross-linking agent using alkylene urea is alkylene A urea-based cross-linking agent or one using benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the thermosetting photosensitive composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. and a melamine-based cross-linking agent.

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

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

Specific examples of benzoguanamine cross-linking agents include monohydroxymethylated benzoguanamine and dihydroxymethylated benzoguanamine. trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

Other compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups include at least one group selected from the group consisting of methylol groups and alkoxymethyl groups on an aromatic ring (preferably a benzene ring). Compounds in which groups are directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4′,4″-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5 ,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3′,5,5′-tetrakis ( methoxymethyl)-1,1'-biphenyl-4,4'-diol and the like.

Commercial products may be used as the thermal cross-linking agent, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP- Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML- BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Kogyo Co., Ltd.), Nikalac (registered trademark, hereinafter the same) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) etc.

The thermosetting photosensitive composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as a thermal crosslinking agent.

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the thermosetting photosensitive composition.

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822, 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, Ricaresin (registered trademark) BEO-20E (the above products name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark) L-200 (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) Trademark) 2000, EHPE3150, Epolead (registered trademark) GT401, Epolead (registered trademark) GT401, Epolead (registered trademark) PB4700, Epolead (registered trademark) PB3600 (trade 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, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN- 502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade names, manufactured by Nippon Kayaku Co., Ltd.) and the like. . Among these, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing warpage and being excellent in heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Ricaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

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

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

Preferable examples of benzoxazine compounds include Ba type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, Fa type benzoxazine (trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly 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 the thermal cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. , more preferably 0.5 to 15% by mass, particularly preferably 1.0 to 10% by mass. One type of thermal cross-linking agent may be contained, or two or more types may be contained. When two or more thermal cross-linking agents are contained, the total is preferably within the above range.

<Compound having sulfonamide structure, compound having thiourea structure>
From the viewpoint of improving the adhesion of the resulting cured film to the substrate, the thermosetting photosensitive composition of the present invention contains at least It preferably further comprises one compound.

式（Ｓ－１）中、Ｒは水素原子又は有機基を表し、Ｒは他の構造と結合して環構造を形成してもよく、＊はそれぞれ独立に、他の構造との結合部位を表す。
上記Ｒは、下記式（Ｓ－２）におけるＲ^２と同様の基であることが好ましい。
スルホンアミド構造を有する化合物は、スルホンアミド構造を２以上有する化合物であってもよいが、スルホンアミド構造を１つ有する化合物であることが好ましい。[Compound having a sulfonamide structure]
A 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, * each independently represents a bonding site with another structure show.
R above is preferably the same group as R ² in formula (S-2) below.
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.

式（Ｓ－２）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^１、Ｒ^２及びＲ^３のうち２つ以上が互いに結合して環構造を形成していてもよい。
Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、１価の有機基であることが好ましい。
Ｒ^１、Ｒ^２及びＲ^３の例としては、水素原子、又は、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、カルボキシ基、カルボニル基、アリル基、ビニル基、複素環基、若しくはこれらを２以上組み合わせた基などが挙げられる。
上記アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、２－エチルへキシル基等が挙げられる。
上記シクロアルキル基としては、炭素数５～１０のシクロアルキル基が好ましく、炭素数６～１０のシクロアルキル基がより好ましい。上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
上記アルコキシ基としては、炭素数１～１０のアルコキシ基が好ましく、炭素数１～５のアルコキシ基がより好ましい。上記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基及びペントキシ基等が挙げられる。
上記アルコキシシリル基としては、炭素数１～１０のアルコキシシリル基が好ましく、炭素数１～４のアルコキシシリル基がより好ましい。上記アルコキシシリル基としては、メトキシシリル基、エトキシシリル基、プロポキシシリル基及びブトキシシリル基等が挙げられる。
上記アリール基としては、炭素数６～２０のアリール基が好ましく、炭素数６～１２のアリール基がより好ましい。上記アリール基は、アルキル基等の置換基を有していてもよい。上記アリール基としては、フェニル基、トリル基、キシリル基及びナフチル基等が挙げられる。
上記複素環基としては、トリアゾール環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジジン環、ピラジン環、ピペリジン環、ピペリジン、ピペラジン環、モルホリン環、ジヒドロピラン環、テトラヒドロピラン基、トリアジン環等の複素環構造から水素原子を１つ除いた基などが挙げられる。A 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 A ring structure may be formed.
R ¹ , R ² and R ³ are each independently preferably a monovalent organic group.
Examples of R ¹ , R ² and R ³ are 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, an allyl group, a vinyl group, a heterocyclic group, or a group obtained by combining two or more of these can be mentioned.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the heterocyclic group 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 piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazine ring.

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 methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide and the like.

式（Ｔ－１）中、Ｒ^４及びＲ^５はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^４及びＲ^５は結合して環構造を形成してもよく、Ｒ^４は＊が結合する他の構造と結合して環構造を形成してもよく、Ｒ^５は＊が結合する他の構造と結合して環構造を形成してもよく、＊はそれぞれ独立に、他の構造との結合部位を表す。[Compound having a thiourea structure]
A 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 combine to form a ring structure, and R ⁴ is * may be combined with another structure to which * is bonded to form a ring structure, R ⁵ may be combined with another structure to which * is bonded to form a ring structure, * is each independently represents the binding site with the structure of

Each of R ⁴ and R ⁵ is preferably 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, or groups in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the heterocyclic group 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 piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazine ring.
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.

式（Ｔ－２）中、Ｒ^４～Ｒ^７はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^４～Ｒ^７のうち少なくとも２つは互いに結合して環構造を形成していてもよい。A 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 together to form a ring structure. may

In formula (T-2), R ⁴ and R ⁵ have the same definitions 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), preferred embodiments of monovalent organic groups for R ⁶ and R ⁷ are the same as preferred embodiments of monovalent organic groups for 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 thiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, 1,3-dimethyl-2-thiohydantoin and the like.

〔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 thermosetting photosensitive composition of the present invention is preferably from 0.05 to 10% by mass, and from 0.1 to It is more preferably 5% by mass, and even more preferably 0.2 to 3% by mass.
The thermosetting photosensitive composition of the present invention may contain only one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one type 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 preferably falls within the above range.

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

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

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

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

Specific examples of migration inhibitors include the following compounds.

When the thermosetting photosensitive composition has a migration inhibitor, the content of the migration inhibitor is 0.01 to 5.0% by mass with respect to the total solid content of the thermosetting photosensitive composition. is preferred, 0.05 to 2.0 mass % is more preferred, and 0.1 to 1.0 mass % is even more preferred.

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

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

Examples of polymerization inhibitors 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-nitrosophenylhydroxyamine cerium salt, N- Nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl -4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 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 radicals, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxyl Amine ammonium salts and the like are preferably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used.

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

When the thermosetting photosensitive composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor, relative to the total solid content of the thermosetting photosensitive composition of the present invention, for example 0.01 to 20 0% by mass, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and 0.05 to 2.5% by mass. is more preferred. In addition, when storage stability of the photosensitive resin composition solution is required, an aspect of 0.02 to 15.0% by mass is also preferable, and in that case, 0.05 to 10.0% by mass is more preferable. is.

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

<Metal adhesion improver>
The thermosetting photosensitive composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring and the like. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds. etc.

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

Other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 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- Examples include isocyanatopropyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used singly or in combination of two or more.

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

[Aluminum Adhesion Aid]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), 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, still more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

<Other additives>
The thermosetting photosensitive composition of the present invention may contain various additives, such as sensitizers such as N-phenyldiethanolamine, chain transfer agents, and higher fatty acids, as long as the effects of the present invention can be obtained. Derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. can be blended. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the thermosetting photosensitive composition.

[Sensitizer]
The thermosetting photosensitive composition of the present invention may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
Examples of sensitizers include sensitizers such as N-phenyldiethanolamine. In addition, benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, Compounds such as cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds can be used.
For example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6- Bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p- dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3 -bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl Aminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino ) coumarin-3-carboxylate ethyl), N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3′,4′-dimethylacetanilide and the like mentioned.
Moreover, you may use a sensitizing dye as a sensitizer.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.

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

[Chain transfer agent]
The thermosetting photosensitive composition of the invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Jiten, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. Chain transfer agents include, for example, a group of compounds having —S—S—, —SO ₂ —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation chain Transfer ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

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

When the thermosetting photosensitive composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 0.01 parts per 100 parts by mass of the total solid content of the thermosetting photosensitive composition of the present invention 20 parts by mass is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is even more preferable. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.

[Higher Fatty Acid Derivative]
In the thermosetting photosensitive composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen, and the composition is heat-cured during the drying process after coating. It may be unevenly distributed on the surface of the photosensitive composition.

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

When the thermosetting photosensitive composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10 mass with respect to the total solid content of the thermosetting photosensitive composition of the present invention. %. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<Restrictions on other contained substances>
The water content of the thermosetting photosensitive 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.

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

In addition, as a method for reducing metal impurities unintentionally contained in the thermosetting photosensitive composition of the present invention, a raw material having a low metal content is used as a raw material constituting the thermosetting photosensitive composition of the present invention. Distillation is carried out under conditions in which contamination is suppressed as much as possible by lining the inside of the device with polytetrafluoroethylene or the like to perform filter filtration on the raw materials constituting the thermosetting photosensitive composition of the present invention. and the like.

Considering the use as a semiconductor material, the thermosetting photosensitive composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, from the viewpoint of wiring corrosion. More preferably less than 200 mass ppm. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.

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

<Application of thermosetting photosensitive composition>
The thermosetting photosensitive composition of the present invention is a composition used for forming a thermosetting photosensitive layer, and is more preferably used for forming a thermosetting photosensitive layer by a slit coating method.
The thermosetting photosensitive composition of the present invention is preferably applied to non-uniform substrates.
The non-uniform base material may be any base material in which the thermosetting photosensitive layer does not have a uniform thickness when the thermosetting photosensitive layer is formed on the base material. The surface of the substrate, such as a substrate having an uneven physical shape on the surface of the substrate, such as a substrate having a base materials having non-uniform chemical properties.
The substrate having a stepped surface means a substrate having a stepped surface, and may be a substrate having an uneven surface.
A base material having an inclined surface means a base material having an inclined surface on at least a part thereof, and may be a base material having an uneven surface.
Substrates with non-uniform chemical properties on the surface of the substrate, such as only a part of the surface is difficult to mix with the composition, include, for example, substrates with different materials on a part of the surface of the substrate, Even if the surface is flat, any substrate on which a thermosetting photosensitive layer having a uniform thickness is not formed may be used. Examples of a base material having a part of the base material surface different in material include a base material having an insulating layer and conductor wiring on the surface of the base material.
The difference in height between the rearmost part and the lowest part of a substrate whose physical shape on the surface of the substrate is not uniform (substrate whose surface height is not uniform) is the average thickness of the thermosetting photosensitive layer It is preferably 5 to 90%, more preferably 10 to 80%, even more preferably 12 to 60% of the weight.
The form of the surface of the substrate whose physical shape is not uniform is not particularly limited. , a trough shape or a saddle shape, a shape having a height difference in the thickness direction, such as a shape that is high or low in the thickness direction.
The difference in height may be a difference due to the shape of the substrate, or may be a difference formed by elements formed on the substrate such as an electrode, an insulating film, etc., and may be formed by anything. is not limited.

The thermosetting photosensitive composition of the present invention is preferably used for forming an interlayer insulating film for rewiring layers.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, or the like.

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

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the thermosetting photosensitive composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less.
The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When performing filtration under pressure, the pressure to be applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , more preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurities may be removed using an adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. A known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, cured films, laminates, semiconductor devices, and manufacturing methods thereof will be described.

The cured film of the present invention is obtained by curing the thermosetting photosensitive composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers of the cured film of the present invention, or three to seven layers may be laminated to form a laminate. It is preferable that the laminate of the present invention contains two or more cured films and a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferred. Both the first cured film and the second cured film are cured films of the present invention, for example, both the first cured film and the second cured film are thermosets of the present invention A preferred embodiment is a film obtained by curing a photosensitive composition. The thermosetting photosensitive composition of the present invention used to form the first cured film and the thermosetting photosensitive composition of the present invention used to form the second cured film have the same composition. or compositions having different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.

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

The cured films according to the invention can also be used in the production of printing plates such as offset or screen printing plates, in the etching of molded parts, in the production of protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a film forming step of applying the thermosetting photosensitive composition of the present invention to a substrate to form a film. preferably included.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a developing step of developing the film.
Moreover, it is more preferable that the method for producing a cured film of the present invention includes a heating step of heating the film.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) A film forming step of applying a thermosetting photosensitive composition to a substrate to form a film (thermosetting photosensitive composition layer) (b) After the film forming step, an exposure step of exposing the film ( c) Development step of developing the exposed film (d) Heating step of heating the developed film By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal acid generator is decomposed, and the generated acid promotes cross-linking of the thermal cross-linking agent, thereby obtaining sufficient curability.

A method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present embodiment, after forming a cured film according to the above method for producing a cured film, the step (a), or the steps (a) to (c), or (a ) to (d) are performed. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferred to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d) ) can be performed a plurality of times to obtain a cured film laminate.

<Film forming step (layer forming step)>
A production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a thermosetting photosensitive composition to a substrate to form a film (layered).

The type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicon substrate and a mold resin substrate are more preferable.
As the base material, for example, a plate-like base material (substrate) is used.

Moreover, when forming a thermosetting photosensitive composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer serves as a base material.

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

Specifically, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. From the viewpoint of uniformity of the thickness of the thermosetting photosensitive composition layer, spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. A slit coating method is preferred. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of the spin coating method, for example, it may be applied at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds, and may be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. can. Moreover, in order to obtain uniformity of the film thickness, it is also possible to apply by combining a plurality of number of revolutions.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.

<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after forming the film (thermosetting photosensitive composition layer) and after the film forming step (layer forming step).
The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 3 minutes to 7 minutes. When the amount of solvent in the photosensitive resin composition solution is large, vacuum drying and heat drying can be combined. A hot plate, a hot air oven, or the like is used for drying by heating, and is not particularly limited.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (thermosetting photosensitive composition layer). The amount of exposure is not particularly defined as long as it can cure the thermosetting photosensitive composition ^. 000 mJ/cm ² irradiation is more preferable.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

In relation to the light source, the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, etc., and (7) YAG laser with second harmonic of 532 nm and third harmonic of 355 nm. For the thermosetting photosensitive composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i lines) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

<Development process>
The production method of the present invention may include a development step of developing (developing the film) the exposed film (thermosetting photosensitive composition layer). By developing, for example, in the case of a negative photosensitive resin composition, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed.

Development is performed using a developer. For example, in the case of a negative photosensitive resin composition, the developer can be used without any particular limitation as long as the unexposed portion (non-exposed portion) is removed.
In the present invention, the case where an alkaline developer is used as the developer is called alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is called solvent development.

In alkaline development, the developer is preferably a developer having an organic solvent content of 10% by mass or less, more preferably 5% by mass or less, more preferably 1% by mass or less, with respect to the total mass of the developer. is more preferred, and a developer containing no organic solvent is particularly preferred.
The developer for alkaline development is more preferably an aqueous solution having a pH of 10-15.
Alkali compounds contained in the developer in alkali development include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, metasilicate. Potassium acid, ammonia, amines, and the like. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide. Among them, alkali compounds containing no metal are preferred, and ammonium compounds are more preferred.
Alkaline compounds may be used alone or in combination of two or more. When two or more alkali compounds are used, the total is preferably within the above range.

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

Organic solvents include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. . ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and , ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons such as toluene, xylene, anisole, etc. Group hydrocarbons, cyclic terpenes such as limonene and the like, and sulfoxides such as dimethyl sulfoxide are suitable.

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

Further, the developer may contain a surfactant.

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

After processing with the developer, rinsing may be carried out.
In the case of solvent development, rinsing is preferably performed with an organic solvent different from the developer. Examples include propylene glycol monomethyl ether acetate. Rinsing time is preferably 5 seconds to 5 minutes. A step of applying both a developer and a rinse may also be included between development and rinsing. The time for the above steps is preferably 1 second to 5 minutes.
In the case of alkali development, rinsing is preferably performed using pure water.
Rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step of heating the developed film (heating step).
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, cyclization of a polyimide precursor or a polybenzoxazole precursor, cross-linking of an unreacted radical cross-linking agent, cross-linking of an unreacted thermal cross-linking agent, etc. 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 150° C. or higher. is more preferable, 160° C. or higher is even more preferable, and 170° C. or higher is even more preferable. The upper limit is preferably 500° C. or lower, more preferably 450° C. or lower, still more preferably 350° C. or lower, even more preferably 250° C. or lower, and 220° C. or lower. Even more preferable.

Heating is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity. Residual stress in the film can be relaxed.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, 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 up to the maximum heating temperature is started. For example, when the thermosetting photosensitive composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying, for example, the temperature of the solvent contained in the thermosetting photosensitive composition It is preferable to gradually raise the temperature from a temperature lower than the boiling point by 30 to 200°C.

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

Particularly when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason for this is not clear, it is thought that the ethynyl groups of the specific resin between the layers are cross-linked with each other at this temperature.

Heating may be done in stages. As an example, the temperature is raised from 25° C. to 180° C. at 3° C./min, held at 180° C. for 60 minutes, heated from 180° C. to 200° C. at 2° C./min, and held at 200° C. for 120 minutes. , may be performed. The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to carry out treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, pretreatment step 1 may be performed at 100 to 150°C, and then pretreatment step 2 may be performed at 150 to 200°C.

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

The heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or in a vacuum, 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.

<Metal layer forming step>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (thermosetting photosensitive composition layer).

The metal layer is not particularly limited, and existing metal species can be used. Copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified. More preferred.

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

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

<Lamination process>
Preferably, the production method of the present invention further includes a lamination step.

The lamination step means that the surface of the cured film (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step. , in that order. However, only the film forming step (a) may be repeated. Also, (d) the heating step may be performed collectively at the end or in the middle of lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the laminated thermosetting photosensitive composition layer may be cured at once by heating (d). . In addition, after the (c) development step, (e) a metal layer forming step may be included, and even if the heating of (d) is performed each time at this time, after stacking a predetermined number of times, (d) is collectively performed. Heating may be performed. Needless to say, the lamination step may further include the drying step, the heating step, and the like as appropriate.

After the lamination step, when the lamination step is further performed, a surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. A plasma treatment is exemplified as the surface activation treatment.

The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

For example, the resin layer structure is preferably 3 to 7 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably 3 to 5 layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the thermosetting photosensitive composition so as to cover the metal layer after providing the metal layer. Specifically, (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are repeated in this order, or (a) film formation (b) the exposure step, (c) the development step, and (e) the metal layer formation step, and the step (d) is collectively provided at the end or in the middle. By alternately laminating the thermosetting photosensitive composition layer (resin layer) and the metal layer forming step, the thermosetting photosensitive composition layer (resin layer) and the metal layer are alternately laminated. be able to.

The invention also discloses a semiconductor device comprising the cured film or laminate of the invention. Specific examples of a semiconductor device using the thermosetting photosensitive composition of the present invention for forming an interlayer insulating film for a rewiring layer include the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. , the contents of which are incorporated herein.

EXAMPLES The present invention will be described more specifically 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 gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Synthesis Example 1>
[PIP-1: Polyimide precursor PIP from oxydiphthalic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate Synthesis of -1]
10.00 g (32.3 mmol) of oxydiphthalic dianhydride (dried at 140° C. for 12 hours) and 9.48 g (32.3 mmol) of 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, 100 g of diglyme (diethylene glycol dimethyl ether) and stirred at a temperature of 60° C. for 18 hours to obtain the diester of pyromellitic acid and 2-hydroxyethyl methacrylate, and 3,3′,4,4′-biphenyltetracarboxylic dianhydride. produced a diester of The reaction mixture was cooled to -10.degree. C. and 16.12 g (135.5 mmol) of _SOCl.sub.2 was added over 10 minutes while maintaining the temperature at -10.+-.4.degree. Viscosity increased during SOCl ₂ addition. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was then added to the reaction mixture over 20 minutes while maintaining the temperature between -5 and 0°C. Dripped. Then, the solution and the reaction mixture were allowed to react at 0° C. for 1 hour, then 70 g of ethanol was added, and the mixture was stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the resulting polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain polyimide precursor PIP-1.

<Synthesis Example 2>
[PIP-2: Synthesis of polyimide precursor PIP-2 from oxydiphthalic dianhydride, 4,4′-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]
In the synthesis of the polyimide precursor PIP-1 above, 10.00 g (32.3 mmol) of oxydiphthalic dianhydride and 9.48 g (32.3 mmol) of 3,3′,4,4′-biphenyl Polyimide precursor PIP-2 was prepared in the same manner as the synthesis of polyimide precursor PIP-1, except that the tetracarboxylic dianhydride was changed to 20.01 g (64.5 mmol) of oxydiphthalic dianhydride. Synthesized.

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

<Synthesis Example 4>
[PI-2: Polyimide from oxydiphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane Synthesis of PI-2]
In the synthesis of polyimide PI-1, "After cooling the above reaction solution to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. To this solution, 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added. It was added dropwise and stirred at 25° C. for 2 hours, and then 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. , polyimide PI-2 was synthesized in the same manner as the synthesis of polyimide PI-1.

<Synthesis Example 5>
[Synthesis of polybenzoxazole precursor PBP-1 from 4,4′-oxydibenzoyl chloride and 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane]
28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was added to 75 g of N-methylpyrrolidone while maintaining the temperature at -10 to 0°C. The dissolved solution was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added and stirred for an additional 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor PBP-1 was then dried under reduced pressure at 45° C. for 3 days.

<Synthesis Example 6>
[Synthesis of polybenzoxazole PB-1 from 4,4′-oxydibenzoyl chloride and 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane]
The above polybenzoxazole precursor PBP-1 was dissolved in 300 g of N-methylpyrrolidone (NMP), heated to 180° C. while flowing nitrogen at a flow rate of 200 ml/min, and stirred for 6 hours. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio) and stirred for 30 minutes at a speed of 2,000 rpm. The precipitated polybenzoxazole was collected by filtration, spray-washed with 1.5 liters of water, filtered off, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again to obtain polybenzoxazole. The resulting polybenzoxazole was dried under reduced pressure at 40° C. for 1 day to obtain polybenzoxazole PB-1.

<Examples and Comparative Examples>
In each example, the components shown in Table 1, Table 2 or Table 3 below were mixed to obtain each thermosetting photosensitive composition. In addition, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition.
Specifically, the contents of the components shown in Table 1, Table 2, or Table 3 were the amounts shown in "parts by mass" in Table 1, Table 2, or Table 3. In addition, in each composition, the content of the solvent was adjusted so that the solid content concentration of the composition was the value shown in Table 1, Table 2 or Table 3.
The description in the "metal concentration" column in Table 1, Table 2 or Table 3 represents the metal content (mass ppm) relative to the total mass of the composition.
In Table 1, Table 2 or Table 3, for example, the description of "C-1/C-3" and "0.07/0.03" in the surfactant column indicates that C-1 is 0.07 parts by mass, This indicates that 0.03 parts by mass of C-3 was used.
The resulting thermosetting photosensitive composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
Also, in Table 1, Table 2 or Table 3, the description of "-" indicates that the composition does not contain the corresponding component.

The details of each component described in Table 1, Table 2 or Table 3 are as follows.

[Specific resin]
・PIP-1 to PIP-2: PIP-1 to PIP-2 synthesized above
・ PI-1 to PI-2: PI-1 to PI-2 synthesized above
· PBP-1: PBP-1 synthesized above
· PB-1: PB-1 synthesized above

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

[Surfactant]
・ C-1: PF-6320 (manufactured by Kitamura Chemical Industry Co., Ltd.)
・ C-2: KF-6048 (manufactured by Shin-Etsu Silicone Co., Ltd.)
・ C-3: acetylenol E00 (manufactured by Kawaken Fine Chemicals Co., Ltd.)
・ C-4: Adekatol LA-775 (manufactured by ADEKA Co., Ltd.)
・ C-5: ADEKA Estol S-20 (manufactured by ADEKA Co., Ltd.)
・ C-6: ADEKA COAL PS-440E (manufactured by ADEKA Co., Ltd.)
・ C-7: Adekatol PC-6 (manufactured by ADEKA Co., Ltd.)

上記Ｄ－３は、国際公開第２０１７／２１７２９２号に記載の合成方法に従い合成した。[Photosensitive agent]
・ D-1: IRGACURE OXE 01 (manufactured by BASF)
・ D-2: ADEKA NCI-930 (manufactured by ADEKA Co., Ltd.)
・D-3: A compound having the following structure (the description of 2:1 represents the molar ratio of each structure.)

The above D-3 was synthesized according to the synthetic method described in WO 2017/217292.

[Thermal cross-linking agent]
・ E-1: Nikarak MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

〔Silane coupling agent〕
・ F-1: N-(3-(triethoxysilyl) propyl) phthalamic acid ・ F-2: IM-1000 (manufactured by JX Metals Co., Ltd.)
・ F-3: benzophenone-3,3′-bis(N-(3-triethoxysilyl)propylamide)-4,4′-dicarboxylic acid

[Thermal base generator]
・G-1: a compound having the following structure

[Polymerization inhibitor]
· H-1: 2-nitroso-1-naphthol · H-2: 4-methoxy-1-naphthol · H-3: benzoquinone

〔Additive〕
・I-1: N-phenyldiethanolamine ・I-2: 1,3-dibutylthiourea ・I-3: 1H-tetrazole

〔solvent〕
・J-1: N-methyl-2-pyrrolidone ・J-2: γ-butyrolactone ・J-3: Ethyl lactate ・J-4: Dimethyl sulfoxide The description in the column indicates the content (% by mass) of each solvent with respect to the total mass of the solvent.

<Evaluation>
[Measurement of surface free energy]
In each example and comparative example other than Examples 23 and 24, respectively, the thermosetting photosensitive composition or the comparative composition was applied onto a flat 4-inch silicon wafer by a slit coating method, and on a hot plate, Dried at 80 ° C. for 5 minutes, a thermosetting photosensitive layer A having a thickness of 150% of the thickness described in the "Thickness (μm)" column of Table 1, Table 2 or Table 3, and Table 1, a thermosetting photosensitive layer B having a film thickness of 50% of the thickness described in the "Thickness (μm)" column of Table 2 or Table 3 was formed.
In Examples 23 and 24, the coating method was changed from the slit coating method to the spin coating method, and the same thermosetting photosensitive layer A and thermosetting photosensitive layer B as in Examples 1 to 22 were formed.
In each example and comparative example, the thermosetting photosensitive layer A was heated at 250° C. for 120 minutes to prepare a cured film A. Then, the contact angle of water and the contact angle of diiodomethane of the cured film A were measured, and the surface free energy A (mJ/m ² ) was calculated from these contact angles using the formula (1).
In each example and comparative example, the surface free energy B (mJ/m ² ) of the thermosetting photosensitive layer B was calculated in the same manner as the surface free energy A was calculated.
In the column of "absolute value of surface free energy difference" in Table 1, Table 2 or Table 3, the absolute value (mJ/m ² ) of the difference between the surface free energy A and the surface free energy B is described.
In the column of "Surface free energy of cured film A" in Table 1, Table 2 or Table 3, the value of surface free energy A (mJ/m ² ) is described.
In the column of "absolute value/surface free energy of cured film A" in Table 1, Table 2 or Table 3, the difference between the surface free energy A and the surface free energy B with respect to the value of the surface free energy A The percentage of absolute value (percentage, %) is described.

[Evaluation of substrate step suitability]
An OFPR (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) film, which is a photoresist, is formed on an 8-inch round silicon wafer, and photolithography is used to form grooves of 30 μm in length, 30 μm in width, and 4 μm in depth. A pattern is formed in which steps are repeated every 50 μm in both the vertical and horizontal directions, and dry etching is performed using an etching apparatus (RIE-10N manufactured by Samco) using this pattern as a mask, resulting in a pattern made of OFPR. was peeled off with acetone to form a step with a depth of 4 μm to obtain a stepped substrate.
In each of the Examples and Comparative Examples other than Examples 23 and 24, the resin layer 1 was formed by applying the thermosetting photosensitive composition or the comparative composition to the stepped substrate by a slit coating method.
In Examples 23 and 24, the resin layer 1 was formed by applying the thermosetting photosensitive composition onto the stepped substrate by spin coating.
The stepped substrate to which the obtained resin layer 1 is applied is dried on a hot plate at 80 ° C. for 5 minutes, and the average thickness is shown in Table 1, Table 2 or Table 3 "Film thickness (μm) , was obtained.
Thereafter, the entire surface of the obtained thermosetting photosensitive layer 1 was exposed to i-rays at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The stepped substrate on which the exposed thermosetting photosensitive layer 1 was formed was heated on a hot plate at 100° C. for 5 minutes.
The exposed thermosetting photosensitive layer 1 was heated in a nitrogen atmosphere at a heating rate of 10° C./min to reach the temperature indicated in the "curing temperature" column of Table 1, Table 2 or Table 3. After that, the film was heated while being maintained at the temperature described in the column of "curing temperature" for the "curing time" in Table 1, Table 2 or Table 3, and a cured film 1 was obtained.
A composition similar to the thermosetting photosensitive composition or the comparative composition used for forming the resin layer 1 was again applied to the surface of the obtained cured film 1 by a slit coating method to form a resin layer 2. .
The obtained stepped substrate to which the resin layer 2 is applied is dried on a hot plate at 80° C. for 5 minutes, and the thickness is described in the “Film thickness (μm)” column of Table 1, Table 2 or Table 3 on the stepped substrate. A thermosetting photosensitive layer 2 having an average thickness of . The thermosetting photosensitive layer 2 was subjected to i-line exposure and heating in the same manner as the thermosetting photosensitive layer 1 to obtain a cured film 2 .
On the surface of the obtained cured film 2 opposite to the cured film 1, the presence or absence of striations (streak-like unevenness) was confirmed, and the surface roughness Ra was measured, and evaluated according to the following evaluation criteria.
The surface roughness Ra of the cured film 2 was measured using an atomic force microscope Dimension FastScan AFM (manufactured by Bruker), and measured 50 μm×50 μm on the surface of the cured film 2 including a portion with a step and a portion without a step vertically. was obtained by measuring the range of
The evaluation results are shown in Table 1, Table 2, or Table 3 in the column of "substrate step suitability".
It can be said that the occurrence of coating defects is suppressed when the occurrence of striations is not observed and the surface roughness Ra is small.

-Evaluation criteria-
A: No striation was observed, and the surface roughness Ra was less than 3 μm.
B: No striation was observed, and the surface roughness Ra was 3 μm or more.
C: Striation was observed.

[Evaluation of Pattern Formability]
In each of the Examples and Comparative Examples other than Examples 23 and 24, the resin layer 1 was formed by applying the thermosetting photosensitive composition or the comparative composition to the stepped substrate by a slit coating method.
In Examples 23 and 24, the resin layer 1 was formed by applying the thermosetting photosensitive composition onto the stepped substrate by spin coating.
The stepped substrate having the resin layer formed thereon was dried on a hot plate at 80° C. for 5 minutes, and the average thickness described in the “Thickness (μm)” column of Table 1, Table 2 or Table 3 was applied to the stepped substrate. A thermosetting photosensitive layer 1 having a thickness was formed.
Thereafter, the entire surface of the obtained thermosetting photosensitive layer 1 was exposed to i-rays at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The stepped substrate on which the exposed thermosetting photosensitive layer 1 was formed was heated on a hot plate at 100° C. for 5 minutes.
The exposed thermosetting photosensitive layer 1 was heated in a nitrogen atmosphere at a heating rate of 10° C./min to reach the temperature indicated in the "curing temperature" column of Table 1, Table 2 or Table 3. After that, the film was heated while being maintained at the temperature described in the column of "curing temperature" for the "curing time" in Table 1, Table 2 or Table 3, and a cured film 1 was obtained.
A composition similar to the thermosetting photosensitive composition or the comparative composition used for forming the resin layer 1 was again applied to the surface of the obtained cured film 1 by a slit coating method to form a resin layer 2. .
The obtained stepped substrate to which the resin layer 2 is applied is dried on a hot plate at 80° C. for 5 minutes, and the thickness is described in the column of “Thickness (μm)” in Table 1, Table 2 or Table 3 on the stepped substrate. A thermosetting photosensitive layer 2 having an average thickness of .
The thermosetting photosensitive layer 2 was exposed using a stepper (Nikon NSR 2005 i9C) to obtain a thermosetting photosensitive layer after exposure. Exposure was performed using i-line, and the exposure amount at a wavelength of 365 nm was 400 mJ/cm ² . A photomask having a 1:1 line-and-space pattern with a line width of 10 μm was used. Exposure was performed so that the line-and-space pattern crossed the stepped portion.
The stepped substrate on which the exposed thermosetting photosensitive layer 2 was formed was heated on a hot plate at 100° C. for 5 minutes.
For the example described as "K-1" in the "developer" column of Table 1, Table 2 or Table 3, cyclopentanone was used for 60 seconds for the thermosetting photosensitive layer 2 after exposure. It was developed and rinsed with PGMEA for 20 seconds to obtain a layer pattern. For the examples described as "K-2" in the "developer" column of Table 1, Table 2 or Table 3, development was performed for 5 minutes using a 2.38% by mass tetramethylammonium hydroxide aqueous solution, followed by pure A layer pattern was obtained by rinsing with water for 20 seconds.
The layer pattern (line pattern) after the development was observed using a scanning electron microscope (SEM) and evaluated according to the following evaluation criteria.
It can be said that the closer the pattern is to a rectangle, the more excellent the pattern formability is, without the occurrence of pattern collapse or residue.

-Evaluation criteria-
A: A rectangular pattern was obtained without pattern collapse or residue.
B: Pattern collapse and residue did not occur, but the pattern was not rectangular.
C: Pattern collapse or residue occurred.

From the above results, a cured film containing at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors, a photosensitizer, a surfactant and a solvent according to the present invention, Absolute difference between the surface free energy of cured film A and the surface free energy of cured film B calculated using formula (1) from the contact angle of water and the contact angle of diiodomethane with respect to the surface of A and the surface of cured film B According to the thermosetting photosensitive composition whose value is 30% or less of the surface free energy of the cured film A, it is applied to a non-uniform substrate to prepare a cured film, and on the resulting cured film It can be seen that the occurrence of defects in other layers is suppressed even when other layers are further formed.
The thermosetting photosensitive compositions according to Comparative Examples 1 and 2 do not contain a surfactant agent.
In the thermosetting photosensitive composition according to Comparative Example 3, the absolute value of the difference between the surface free energy of the cured film A and the surface free energy of the cured film B exceeds 30% of the surface free energy of the cured film A.
The thermosetting photosensitive compositions according to Comparative Examples 1 to 3 are applied to a non-uniform substrate to prepare a cured film, and another layer is further formed on the obtained cured film. It can be seen that the occurrence of defects in the other layers is not suppressed when the thickness is increased.

<Example 101>
The thermosetting photosensitive composition used in Example 1 is applied to the surface of the thin copper layer of the resin substrate having the thin copper layer formed on the surface by a spin coating method, and dried at 80° C. for 5 minutes. After forming a thermosetting photosensitive composition layer with a film thickness of 30 μm, exposure was performed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). 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, the layer was patterned by developing with cyclopentanone for 60 seconds and rinsing with PGMEA for 20 seconds.
Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./min, reaching 180° C., and then maintained at 180° C. for 120 minutes to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layer was excellent in insulating properties.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

Claims (16)

A thermosetting photosensitive composition used for forming a thermosetting photosensitive layer,
at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors;
photosensitizer,
a surfactant, and
contains solvents,
The surface free energy of the cured film A below and the surface free energy of the cured film B below calculated using the following formula (1) from the contact angle of water and the contact angle of diiodomethane on the surface of the cured film A below and the surface of the cured film B below, respectively. The absolute value of the surface free energy difference is 30% or less of the surface free energy of the cured film A below,
In the polyimide precursor, 90 mol% or more of all repeating units are repeating units represented by formula (2),
The photosensitizer is a photoradical polymerization initiator,
Used for forming a thermosetting photosensitive layer by slit coating method or spin coating method
a thermosetting photosensitive composition;
Cured film A: When a coating film of the thermosetting photosensitive composition is formed on a flat support in a thickness of 150% of the average thickness of the thermosetting photosensitive layer and then heated at 250° C. for 120 minutes. A cured film of the thermosetting photosensitive composition obtained in;
Cured film B: When a coating film of the thermosetting photosensitive composition is formed on a flat support in a thickness of 50% of the average thickness of the thermosetting photosensitive layer and then heated at 250° C. for 120 minutes. A cured film of the thermosetting photosensitive composition obtained in;

In the above formula (1), γ _s ^d is the dispersion component of the surface free energy of the cured film, γ _sh is the polar component of the surface free energy of the cured film, and γ _L ^d is the dispersion of ^the surface free energy of water or diiodomethane. γ _L ^h is the polar component of the surface free energy of water or diiodomethane, γ _L
^total represents the surface free energy of water or diiodomethane, and cos θ represents the contact angle of water or diiodomethane;
Here, the surface free energy is represented by the ^sum of the dispersive component and the polar component ^. The dispersive component of the surface free energy of diiodomethane is 48.1 mJ/m ² and the polar component of the surface free energy of diiodomethane is 1.3 mJ/m 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. 2. The thermosetting photosensitive composition according to claim 1, further comprising a radical cross-linking agent. A thermosetting photosensitive composition used for forming a thermosetting photosensitive layer,
at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors;
photosensitizer,
surfactant,
a radical cross-linking agent, and
contains solvents,
The surface free energy of the cured film A below and the surface free energy of the cured film B below calculated using the following formula (1) from the contact angle of water and the contact angle of diiodomethane on the surface of the cured film A below and the surface of the cured film B below, respectively. The absolute value of the surface free energy difference is 30% or less of the surface free energy of the cured film A below,
The surface free energy of the cured film A is 20 mJ/m ² and
In the polyimide precursor, 90 mol% or more of all repeating units are repeating units represented by formula (2),
a thermosetting photosensitive composition;
Cured film A: When a coating film of the thermosetting photosensitive composition is formed on a flat support in a thickness of 150% of the average thickness of the thermosetting photosensitive layer and then heated at 250° C. for 120 minutes. A cured film of the thermosetting photosensitive composition obtained in;
Cured film B: When a coating film of the thermosetting photosensitive composition is formed on a flat support in a thickness of 50% of the average thickness of the thermosetting photosensitive layer and then heated at 250° C. for 120 minutes. A cured film of the thermosetting photosensitive composition obtained in;

In the above formula (1), γ _s ^d is the dispersion component of the surface free energy of the cured film, and γ _s ^h is the polar component of the surface free energy of the cured film, and γ _L. ^d is the dispersion component of the surface free energy of water or diiodomethane, and γ _L. ^h is the polar component of the surface free energy of water or diiodomethane, and γ _L.
^total is the surface free energy of water or diiodomethane, and cos θ is the contact angle of water or diiodomethane;
Here, the surface free energy is represented by the sum of the dispersive component and the polar component, and the dispersive component of the surface free energy of water is 21.7 mJ/m ² , the polar component of the surface free energy of water is 50.8 mJ/m ² , the dispersion component of the surface free energy of diiodomethane is 48.1 mJ/m ² , the polar component of the surface free energy of diiodomethane is 1.3 mJ/m ² and
formula (2)

In formula (2), A ¹ and A ² each independently represents an oxygen atom or NH, and R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group. 4. The thermosetting photosensitive composition according to claim 3, which is used for forming a thermosetting photosensitive layer by slit coating or spin coating. 5. The thermosetting photosensitive composition according to any one of claims 1 to 4 , wherein the content of said surfactant is more than 0.1 wt% relative to the total weight of the composition. 5. The thermosetting photosensitive composition according to any one of claims 1 to 4 , wherein the surfactant content is less than 0.005% by weight relative to the total weight of the composition. The thermosetting photosensitive composition according to any one of claims 1 to 6 , wherein the surfactant comprises a surfactant free of fluorine atoms and silicon atoms. The thermosetting photosensitive material according to any one of claims 1 to 7 , wherein the content of the hydrocarbon surfactant in the composition is 50% by mass or more with respect to the total content of the surfactant. sex composition. 9. The thermosetting photosensitive composition according to any one of claims 1 to 8 , wherein the resin comprises at least one resin selected from the group consisting of polyimides and polyimide precursors. 10. The thermosetting photosensitive composition according to any one of claims 1 to 9 , which is used for forming an interlayer insulating film for rewiring layers. A cured film obtained by curing the thermosetting photosensitive composition according to any one of claims 1 to 10 . A laminate comprising two or more layers of the cured film according to claim 11 and comprising a metal layer between any of the cured films. A method for producing a cured film, comprising a film forming step of applying the thermosetting photosensitive composition according to any one of claims 1 to 10 to a substrate to form a film. 14. The method for producing a cured film according to claim 13 , comprising an exposure step of exposing the film and a developing step of developing the film. The method for producing a cured film according to claim 13 or 14 , comprising a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 11 or the laminate according to claim 12 .