TW202110955A - Thermosetting photosensitive composition, cured film, multilayer body, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a thermosetting photosensitive composition, a cured film formed by curing the above-mentioned thermosetting photosensitive composition, a laminate including the above-mentioned cured film, a method of manufacturing the above-mentioned cured film, and the above-mentioned cured film or the above Laminated semiconductor device, the above-mentioned thermosetting photosensitive composition is used to form a thermosetting photosensitive layer and contains a specific resin, photosensitizer, surfactant, and solvent, the surface free energy of the specific cured film A and the specific curing The absolute value of the difference in the surface free energy of the film B is 30% or less of the surface free energy of the cured film A described above.

Description

Method for manufacturing thermosetting photosensitive composition, cured film, laminate, cured film, and semiconductor device

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

Resins such as polyimide and polybenzoxazole are excellent in heat resistance and insulating properties, so they can be used in various applications. The use is not particularly limited, but if a semiconductor device for actual mounting is taken as an example, the use as a material for an insulating film or a sealing material or a protective film can be cited. It is also used as a base film or cover film for flexible substrates.

For example, in the above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of a thermosetting photosensitive composition containing these resins or their precursors. For example, the thermosetting photosensitive composition is applied to a substrate by coating or the like, and then exposed, developed, heated, etc. as necessary, whereby a hardened resin can be formed on the substrate. The thermosetting photosensitive composition can be applied by a well-known coating method. Therefore, it can be said that, for example, the shape, size, and application position of the thermosetting photosensitive composition to be applied have a high degree of freedom in design, and it is suitable for manufacturing. Excellent performance. From the viewpoint of excellent manufacturing adaptability in addition to the high performance possessed by polyimines, polybenzoxazoles, etc., it is increasingly expected that thermosetting photosensitive compositions containing these resins or their precursors Industrial application expansion.

For example, Patent Document 1 describes a photosensitive resin composition containing: (a) a polyimide resin or its precursor, (b) a quinonediazide compound, (c) a solvent, and (d) Surfactants, (d) surfactants include (d1) silicon-based surfactants and (d2) surfactants having fluorine atoms, and the content of (d1) in the photosensitive resin composition is X mass%, When the content of (d2) is Y mass %, X>Y (Y≠0), and (d) the total amount of surfactant in the photosensitive resin composition is 0.005 mass% or more and 0.10 mass% or less.

[Patent Document 1] JP 2010-243748 A

The thermosetting photosensitive composition comprising at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor is applied to When a hardened film is made on a base material, other layers such as a thermosetting photosensitive layer may be further formed on the obtained hardened film. In addition, as a base material to which this thermosetting photosensitive composition is applied, a base material having unevenness such as a step may be used. Therefore, it is desired to provide a thermosetting photosensitive composition in which a cured film is formed even if it is applied to a non-uniform substrate with a step, etc., and further formed on the obtained cured film. When there are other layers, defects can also be suppressed on other layers.

The object of the present invention is to provide a thermosetting photosensitive composition, a cured film formed by curing the thermosetting photosensitive composition, a laminate including the cured film, a method of manufacturing the cured film, and the cured film. Film or semiconductor device of the above-mentioned laminated body, even if the above-mentioned thermosetting photosensitive composition is applied to a non-uniform substrate to produce a cured film, and another layer is further formed on the obtained cured film, it can be suppressed Defects on the layer.

在上述式（1）中，γ_s ^d 表示硬化膜的表面自由能的分散成分，γ_s ^h 表示硬化膜的表面自由能的極性成分，γ_L ^d 表示水或二碘甲烷的表面自由能的分散成分，γ_L ^h 表示水或二碘甲烷的表面自由能的極性成分，γ_L ^tоtal 表示水或二碘甲烷的表面自由能，cоsθ表示水或二碘甲烷的接觸角； 其中，表面自由能以分散成分與極性成分之和表示，將水的表面自由能的分散成分設為21.7mJ/m² ，將水的表面自由能的極性成分設為50.8mJ/m² ，將二碘甲烷的表面自由能的分散成分設為48.1mJ/m² ，將二碘甲烷的表面自由能的極性成分設為1.3mJ/m² 。 ＜2＞如＜1＞所述之熱硬化性感光性組成物，其中上述界面活性劑的含量相對於組成物的總質量超過0.1質量%。 ＜3＞如＜1＞所述之熱硬化性感光性組成物，其中上述界面活性劑的含量相對於組成物的總質量低於0.005質量%。 ＜4＞如＜1＞～＜3＞之任一項所述之熱硬化性感光性組成物，其中上述界面活性劑係包括不具有氟原子及矽原子之界面活性劑。 ＜5＞如＜1＞～＜4＞之任一項所述之熱硬化性感光性組成物，其中上述組成物中的烴系界面活性劑的含量相對於上述界面活性劑的總含量為50質量%以上。 ＜6＞如＜1＞～＜5＞之任一項所述之熱硬化性感光性組成物，其中上述樹脂包含選自包括聚醯亞胺及聚醯亞胺前驅物之群組中之至少一種樹脂。 ＜7＞如＜1＞～＜6＞之任一項所述之熱硬化性感光性組成物，其係用於基於狹縫塗佈法形成熱硬化性感光層。 ＜8＞如＜1＞～＜6＞之任一項所述之熱硬化性感光性組成物，其係用於基於旋塗法形成熱硬化性感光層。 ＜9＞如＜1＞～＜8＞之任一項所述之熱硬化性感光性組成物，其係用於形成再配線層用層間絕緣膜。 ＜10＞一種硬化膜，其係藉由硬化＜1＞～＜9＞之任一項所述之熱硬化性感光性組成物而成。 ＜11＞一種積層體，其係包含2層以上＜10＞所述之硬化膜，在任意上述硬化膜彼此之間包含金屬層。 ＜12＞一種硬化膜的製造方法，其係包括將＜1＞～＜9＞之任一項所述之熱硬化性感光性組成物適用於基板上來形成膜之膜形成製程。 ＜13＞如＜12＞所述之硬化膜的製造方法，其係包括對上述膜進行曝光之曝光製程及對上述膜進行顯影之顯影製程。 ＜14＞如＜12＞或＜13＞所述之硬化膜的製造方法，其係包括在50～450℃下加熱上述膜之加熱製程。 ＜15＞一種半導體器件，其係包含＜10＞所述之硬化膜或＜11＞所述之積層體。 [發明效果]Hereinafter, examples of representative embodiments of the present invention are shown. <1> A thermosetting photosensitive composition for forming a thermosetting photosensitive layer. The thermosetting photosensitive composition comprises: selected from the group consisting of polyimide, polyimide precursor, and polyphenylene At least one resin in the group of bisazole and polybenzoxazole precursors; photosensitizer; surfactant; and solvent, according to the difference between the surface of the following cured film A and the surface of the following cured film B, respectively The contact angle of water and the contact angle of diiodomethane are calculated using the following formula (1). The absolute value of the difference between the surface free energy of the following cured film A and the surface free energy of the following cured film B is the following cured film 30% or less of the surface free energy of A; Cured film A: The coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 150% of the average thickness of the thermosetting photosensitive layer After that, the cured film of the thermosetting photosensitive composition obtained by heating at 250°C for 120 minutes; Cured film B: The coating film of the thermosetting photosensitive composition is averaged by the average of the thermosetting photosensitive composition After a film thickness of 50% of the thickness is formed on a flat support, the cured film of the above-mentioned thermosetting photosensitive composition is obtained when heated at 250°C for 120 minutes; [Equation 1]

In the above formula (1), γ _s ^d represents the dispersed component of the surface free energy of the cured film, γ _s ^h represents the polar component of the surface free energy of the cured film, and γ _L ^d represents the surface free energy of water or diiodomethane. Dispersion component, γ _L ^h represents the polar component of the surface free energy of _{water or diiodomethane, γ L} ^tоtal represents the surface free energy of water or diiodomethane, and cоsθ represents the contact angle of water or diiodomethane; where, surface free energy Expressed as the sum of the dispersed component and the polar component, the dispersed component of the surface free energy of water is set to 21.7mJ/m ² , the polar component of the surface free energy of water is set to 50.8mJ/m ² , and the surface of diiodomethane The dispersion component of free energy was 48.1 mJ/m ² , and the polar component of the surface free energy of diiodomethane was 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 system includes a surfactant that does not have fluorine atoms and silicon atoms. <5> The thermosetting photosensitive composition according to any one of <1> to <4>, wherein the content of the hydrocarbon-based surfactant in the composition is 50 relative to the total content of the surfactant Above mass%. <6> The thermosetting photosensitive composition according to any one of <1> to <5>, wherein the resin contains at least one selected from the group consisting of polyimine and polyimide precursors A resin. <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 a spin coating method. <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 formed by curing the thermosetting photosensitive composition described in any one of <1> to <9>. <11> A laminate comprising two or more layers of the cured film described in <10>, and a metal layer between any of the cured films. <12> A method for producing a cured film, which includes a film formation process of applying the thermosetting photosensitive composition described in any one of <1> to <9> to a substrate to form a film. <13> The method for producing a cured film as described in <12>, which includes an exposure process for exposing the film and a development process for developing the film. <14> The method for producing a cured film as described in <12> or <13>, which includes a heating process of heating the film at 50 to 450°C. <15> A semiconductor device comprising the cured film described in <10> or the laminated body described in <11>. [Effects of the invention]

According to the present invention, there can be provided a thermosetting photosensitive composition, a cured film formed by curing the thermosetting photosensitive composition, a laminate including the cured film, a method of manufacturing the cured film, and the cured film including the cured film. Film or semiconductor device of the above-mentioned laminated body, even if the above-mentioned thermosetting photosensitive composition is applied to a non-uniform substrate to produce a cured film, and another layer is further formed on the obtained cured film, it can be suppressed Defects on the layer.

Hereinafter, the main embodiment of the benzene invention will be described. However, the present invention is not limited to the illustrated embodiment. In this specification, the numerical range indicated by the symbol "～" means the range that includes the numerical values described before and after the "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only refers to an independent process, but as long as it can achieve the required effect of the process, it also means a process that cannot be clearly distinguished from other processes. Regarding the label of the group (atomic group) in this specification, the label not labeling substituted and unsubstituted includes both a group without a substituent (atomic group) and a group with a substituent (atomic group). For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, "exposure" is not particularly limited, and includes exposure with particle beams such as electron beams and ion beams in addition to exposure with light. In addition, as the light used for exposure, actinic rays or radiations such as the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic" For both or either of them, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components except the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement), and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel can be used Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were obtained as the column. Unless otherwise specified, these molecular weights will be measured using THF (tetrahydrofuran) as the eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV ray (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting the layered body is described as "upper" or "lower", it is only necessary that another layer exists on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, the third layer or the third element may be further sandwiched between the layer serving as the reference and the other layer described above, and the layer serving as the reference does not need to be in contact with the other layer described above. In addition, unless otherwise specified, the direction of the stacked layers of the base material is referred to as "up", or when the photosensitive layer is present, the direction from the base material to the photosensitive layer is referred to as "up", and the opposite direction is referred to as "up". under". In addition, the setting of this vertical direction is for the convenience of this specification. In an actual aspect, the "up" direction in this specification may also be different from the vertical up direction. In this specification, as long as there is no special description, as each component contained in the composition, the composition may contain two or more compounds that conform to the component. In addition, unless otherwise stated, the content of each component in the composition indicates the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C and the air pressure is 101,325 Pa (1 atmosphere). In this specification, a combination of preferred aspects is a more optimal aspect.

(Thermosetting photosensitive composition) The thermosetting photosensitive composition of the present invention is a thermosetting photosensitive composition used to form a thermosetting photosensitive layer, and contains selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and At least one resin in the group of polybenzoxazole precursors (hereinafter, also referred to as “specific resin”), photosensitizer, surfactant, and solvent, according to the relative difference between the surface and the bottom of the cured film A described below The contact angle of the water on the surface of the cured film B and the contact angle of diiodomethane are calculated using the formula (1) to calculate 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 below It is 30% or less of the surface free energy of the cured film A described below. Cured film A: After the coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 150% of the average thickness of the thermosetting photosensitive layer, it is heated at 250°C for 120 minutes The obtained cured film of the above-mentioned thermosetting photosensitive composition Cured film B: After the coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 50% of the average thickness of the thermosetting photosensitive layer, it is heated at 250°C for 120 minutes The obtained cured film of the above-mentioned thermosetting photosensitive composition

As a first aspect, the thermosetting photosensitive composition of the present invention preferably contains a specific resin, a photopolymerization initiator as the above-mentioned photosensitizer, a surfactant, and a solvent. It is preferable that the thermosetting photosensitive composition of the present invention in the first aspect described above further contains a radical crosslinking agent. Moreover, in the above-mentioned first aspect, the aspect further comprising a thermal crosslinking agent is also preferable, and the aspect further comprising a thermal crosslinking agent and a thermal acid generator is also more preferable. As a second aspect, the thermosetting photosensitive composition of the present invention preferably contains a specific resin, a photoacid generator as the above-mentioned photosensitizer, a surfactant, and a solvent. It is preferable that the thermosetting photosensitive composition of the present invention in the second aspect described above further contains a thermal crosslinking agent. The thermosetting photosensitive composition of the present invention may be a negative type thermosetting photosensitive composition or a positive type thermosetting photosensitive composition. The negative thermosetting photosensitive composition is a composition in which the non-exposed part is removed by development during development after exposure. The positive thermosetting photosensitive composition is a composition that is removed by development in the exposed part during development after exposure.

According to the thermosetting photosensitive composition of the present invention, even when a cured film is formed on an uneven substrate and another layer is further formed on the obtained cured film, the occurrence of defects on the other layer can be suppressed. The mechanism for obtaining the above effects is not clear, but it can be presumed as follows.

The thermosetting photosensitive composition is used for the following applications: after applying to a substrate or the like, drying it as necessary to form a thermosetting photosensitive layer, and then obtaining a cured film by heating or the like. In addition, if necessary, for example, patterning can be performed by exposure and development before heating. As a result of intensive research, the inventors found that after forming a thermosetting photosensitive layer on a non-uniform substrate with steps and the like to obtain a cured film, when another layer is further formed on the cured film, there may be other layers. The condition of the defect. There is a solvent in the thermosetting photosensitive layer before drying. Therefore, it is considered that at least a part of the components in the thermosetting photosensitive composition (for example, components that easily move in the composition film such as a surfactant) is applied to the surface of the composition film. mobile. Among them, on non-uniform substrates (for example, substrates with steps on the surface, substrates with slanted surfaces, etc., substrates with non-uniform physical shapes on the surface, or substrates with only part of the surface that are not easily compatible with the composition, etc. When a thermosetting photosensitive layer is formed on a substrate with uneven chemical properties on the surface, the thickness of the thermosetting photosensitive layer may become uneven. For example, on a substrate with a step on the surface, the thermosetting photosensitive layer becomes thinner on the convex portion of the substrate surface, and the thermosetting photosensitive layer becomes thicker on the concave portion of the substrate surface. Also, for example, on a substrate with a tilt on the surface, the thermosetting photosensitive layer becomes thicker at the middle and low tilt portion, and the thermosetting photosensitive layer becomes thinner at the middle and high tilt portion. Furthermore, for example, on a substrate where only a part of the surface is not easily compatible with the composition, in the part that is easily compatible with the composition, the thermosetting photosensitive layer becomes thin due to the easy diffusion of the composition, and it is not easily compatible with the composition. In the compatible part, the thermosetting photosensitive layer becomes thicker because the composition is not easily diffused. The above-mentioned surfactants and other components move from the inside of the thermosetting photosensitive layer. Therefore, it is thought that more of the above-mentioned components move to the surface in the thick part of the thermosetting photosensitive layer, but move to the surface in the thin part of the thermosetting photosensitive layer. The above-mentioned ingredients are less. By curing the thermosetting light-sensitive composition whose distribution of the component is different depending on the position on the surface, as a cured film, and further forming other layers on the cured film, due to the coating properties when forming other layers, etc. It differs depending on the position on the surface of the cured film, so it is thought that defects will occur in other layers. The composition of the present invention is a composition that can obtain a cured film having a small difference in the change of the surface free energy to the film thickness. Therefore, it is presumed that the occurrence of defects in the above-mentioned other layers can be suppressed. Regarding the suppression of the above-mentioned defects, it is considered to be particularly remarkable when forming a thermosetting photosensitive layer by a method such as a slit coating method that requires a long time for drying after coating.

Among them, in Patent Document 1, there is no description or suggestion of a thermosetting photosensitive composition whose difference in surface free energy is a specific value. Hereinafter, the characteristics and the components contained in the thermosetting photosensitive composition of the present invention will be described in detail.

在上述式（1）中，γ_s ^d 表示硬化膜的表面自由能的分散成分，γ_s ^h 表示硬化膜的表面自由能的極性成分，γ_L ^d 表示水或二碘甲烷的表面自由能的分散成分，γ_L ^h 表示水或二碘甲烷的表面自由能的極性成分，γ_L ^tоtal 表示水或二碘甲烷的表面自由能，cоsθ表示水或二碘甲烷的接觸角； 其中，表面自由能以分散成分與極性成分之和表示，將水的表面自由能的分散成分設為21.7mJ/m² ，將水的表面自由能的極性成分設為50.8mJ/m² ，將二碘甲烷的表面自由能的分散成分設為48.1mJ/m² ，將二碘甲烷的表面自由能的極性成分設為1.3mJ/m² 。 硬化膜的表面自由能作為分散成分γ_s ^d 與γ_s ^h 之和求出，具體而言，藉由求解由下述式（R1）及式（R2）表示之聯立方程式來求出。 [數式3]

其中，θ1係水的接觸角，θ2係二碘甲烷的接觸角。<Surface free energy> The thermosetting photosensitive composition of the present invention is based on 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, using the formula (1 ) The calculated 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 becomes 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 by formula (1) based on the contact angle of water and the contact angle of diiodomethane. Specifically, the surface free energy is an energy obtained by contacting the cured film A or cured film B with 1μl of water and diiodomethane to measure the respective contact angles, and is calculated as the value for each contact angle satisfying the following formula . For example, it can be calculated using the functional integration analysis software FAMAS (manufactured by Kyowa Interface Science Co., Ltd.). [Numerical formula 2]

In the above formula (1), γ _s ^d represents the dispersed component of the surface free energy of the cured film, γ _s ^h represents the polar component of the surface free energy of the cured film, and γ _L ^d represents the surface free energy of water or diiodomethane. Dispersion component, γ _L ^h represents the polar component of the surface free energy of _{water or diiodomethane, γ L} ^tоtal represents the surface free energy of water or diiodomethane, and cоsθ represents the contact angle of water or diiodomethane; where, surface free energy Expressed as the sum of the dispersed component and the polar component, the dispersed component of the surface free energy of water is set to 21.7mJ/m ² , the polar component of the surface free energy of water is set to 50.8mJ/m ² , and the surface of diiodomethane The dispersion component of free energy was 48.1 mJ/m ² , and the polar component of the surface free energy of diiodomethane was 1.3 mJ/m ² . The surface free energy of the cured film is _{calculated as the sum of the dispersed components γ s} ^d and γ _s ^h , specifically, by solving the simultaneous equations represented by the following formulas (R1) and (R2). [Numerical formula 3]

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

例如利用橢圓偏光計（Foothill Instruments, LLC製KT-22）測定上述厚度T1、T2、Ti等熱硬化性感光層的厚度。In addition, 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. For example, the area formed by the thermosetting photosensitive layer of thickness T1 is S1, When the area formed by the thermosetting photosensitive layer of thickness T2 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. Average thickness=T1×S1/(S1+S2)+T2×S2/(S1+S2) Similarly, the area of the thermosetting photosensitive layer with n thicknesses of Ti is Si (i is an integer from 1 to n). , S1+S2+・・・+Sn is the total area of the thermosetting photosensitive layer), the above average thickness is calculated by the following formula. [Equation 4]

For example, the thickness of the thermosetting photosensitive layer, such as the above-mentioned thickness T1, T2, and Ti, is measured with an ellipsometer (KT-22 manufactured by Foothill Instruments, LLC).

A surface of the cured film free energy of 10 ~ 50mJ / m ² is preferred, 15 ~ 40mJ / m ² is more preferably, 20 ~ 35mJ / m ² is further preferable. B cured film surface of the free energy of 10 ~ 50mJ / m ² is preferred, 15 ~ 40mJ / m ² is more preferably, 20 ~ 35mJ / m ² is further preferable.

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 of the surface free energy of the cured film A, more preferably 20% or less, and more preferably 10% or less . There is no particular limitation on the lower limit, and it 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, for example It is considered to be determined by the amount of surfactant in the thermosetting photosensitive composition, the type of surfactant, and the like.

The production method of the coating film on the cured film A and the cured film B is not particularly limited, and the method of producing the coating film in the formation of the thermosetting photosensitive layer using the thermosetting photosensitive composition of the present invention is not particularly limited. The same method is better. For example, when the thermosetting photosensitive layer is produced by the slit coating method, the coating films on the cured film A and the cured film B are also preferably produced by the slit coating method.

In addition, in the thermosetting photosensitive composition of the present invention, the absolute value of the difference between the surface free energy of the following cured film C and the surface free energy of the following cured film D is that of the surface free energy of the following cured film C 30% or less is preferable, 20% or less is more preferable, and 10% or less is still more preferable. The lower limit is not particularly limited, as long as 0% or more is sufficient. Cured film C: The coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 45 μm, and then heated at 250°C for 120 minutes. Hardened film Cured film D: The coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 15 μm, and then heated at 250°C for 120 minutes. Hardened film

<Specific resin> The thermosetting photosensitive composition of the present invention contains at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor Resin (specific resin). The specific resin preferably includes at least one resin selected from the group consisting of polyimine and polyimide precursors. Furthermore, it is preferable that the said resin contains a polymerizable group and the photosensitive resin composition contains a polymerizable compound. With this structure, a three-dimensional network is formed in the exposed part to become a strong crosslinked film, and the photosensitive resin composition layer (resin layer) is not easily damaged by the surface activation treatment, and may be damaged by Surface activation treatment is more effective in improving adhesion. In particular, it is effective in terms of adhesion to the upper layer. Furthermore, it is preferable that the polyimide and polybenzoxazole contained in the resin layer in the laminate of the present invention include a partial structure represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO-, Or a group composed of a combination of two or more of the above. With this structure, the resin layer becomes a flexible structure, and the occurrence of peeling can be suppressed more effectively. Ar-based phenylene groups are preferred, and L-based aliphatic hydrocarbon groups with 1 or 2 carbons, -O-, -CO-, -S- or -SO ₂ -which may be substituted by fluorine atoms are preferred. The aliphatic hydrocarbon-based alkylene group is preferred here.

在式（2）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。[Polyimine precursor] The polyimine precursor used in the present invention is not particularly limited in its kind, etc., but preferably contains a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1]

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

^{A 1} and A ² in formula (2) each independently represent an oxygen atom or NH, and an oxygen atom is preferred. ^{R 111} in the formula (2) represents a divalent organic group. Examples of divalent organic groups include groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbons, and carbon A cyclic aliphatic group with 6 to 20, an aromatic group with 6 to 20 carbons, or a group composed of these combinations are preferred, and a group containing an aromatic group with 6 to 20 carbons is more preferred . As a particularly preferred embodiment of the present invention, the case of a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO-, Or a group composed of a combination of two or more of the above. The preferable ranges of these are as described above.

Preferably, R ¹¹¹ is derived from diamine. Examples of diamines used for 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, it contains a linear or branched aliphatic group with 2 to 20 carbons, a cyclic aliphatic group with 6 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination of these The diamine of the group is preferred, and the diamine containing a group composed of an aromatic group having 6 to 20 carbon atoms is more preferred. As an example of the group containing an aromatic group, the following groups can be mentioned.

式中，A係單鍵或可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO₂ -及-NHCO-、以及選自該等的組合之基團為較佳，單鍵或選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-、-SO₂ -中之基團為更佳，選自包括-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之群組中之2價基團為進一步較佳。[Chemical formula 2]

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

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone 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, double (3-Amino-4-hydroxyphenyl) arsenic, bis(4-amino-3-hydroxyphenyl) arsenic, 4,4'-diamino-p-terphenyl, 4,4'-bis(4- Aminophenoxy) biphenyl, bis[4-(4-aminophenoxy)phenyl] chrysene, bis[4-(3-aminophenoxy) phenyl] chrysene, bis[4-( 2-aminophenoxy) phenyl] chrysene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-bis Methyl-4,4'-diaminodiphenyl benzene, 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'-di Aminodiphenylmethane, 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-amino Phenyl) Sulfonium, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3,3',5,5'-tetramethyl-4,4'-diaminodi Phenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester 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]hexa Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-di Methylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4- Amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amine 3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3 -Amino-5-trifluoromethylphenoxy)diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2 , At least one diamine of 2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminotetrabiphenyl.

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

[Chemical formula 3]

[Chemical formula 4]

Moreover, as a preferable example, the diamine which has at least 2 or more alkylene glycol units in a main chain can also be mentioned. More preferably, a diamine containing two or more of ethylene glycol chains and propylene glycol chains or both of them in total is more preferable in one molecule, and it is more preferable that the diamine is the above-mentioned diamine and does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D- 4000 (above trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1- (2-Aminopropoxy)propan-2-yl)oxy)propane-2-amine and the like, but are not limited to these. The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Chemical formula 5]

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

From the viewpoint of the flexibility of the cured film obtained, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO-, Or a group composed of a combination of two or more of the above. Ar-based phenylene groups are preferred, and L-based aliphatic hydrocarbon groups with 1 or 2 carbons, -O-, -CO-, -S- or -SO ₂ -which may be substituted by fluorine atoms are preferred. The aliphatic hydrocarbon-based alkylene group is preferred here.

在式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價有機基團，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R⁵⁰ ～R⁵⁷ 的1價有機基團，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式7]

在式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出2,2'-二甲對聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用一種或組合兩種以上來使用。From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by formula (61) is more preferable. Formula (51) [Chemical Formula 6]

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 trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in formula (2). ^Examples of the monovalent organic groups of R ⁵⁰ to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably carbons 1～6) Fluorinated alkyl groups, etc. [Chemical formula 7]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group. Examples of the diamine compound imparting the structure of formula (51) or (61) include 2,2'-dimethylparabenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used singly or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical formula 8]

在式（5）中，R¹¹² 表示單鍵或可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -及-NHCO-、以及選自該等的組合之基團為較佳，單鍵或選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之群組中之2價基團為進一步較佳。 ^{R 115} in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. Formula (5) [Chemical Formula 9]

In the formula (5), R ¹¹² represents a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -and -NHCO-, And a group selected from a combination of these is preferred, a single bond or a C1-C3 alkylene group that can be substituted by a fluorine atom, -O-, -CO-, -S- and -SO ₂ The group in-is more preferred, and is selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ The divalent group in the group of-is further preferred.

Formula (6) [Chemical Formula 10]

在式（O）中，R¹¹⁵ 表示4價有機基團。R¹¹⁵ 的較佳範圍的含義與式（2）中的R¹¹⁵ 相同，較佳範圍亦相同。Specifically, R ¹¹⁵ includes the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical formula 11]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The same (2) R ¹¹⁵ R ¹¹⁵ is preferably in the range of meaning as in formula, preferred ranges are also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' -Biphenyltetracarboxylic dianhydride, 2,3,3',4'-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-perylene Tetracarboxylic 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-benzene Tetracarboxylic dianhydride and these C1-C6 alkyl groups and C1-C6 alkoxy derivatives.

Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below can also be mentioned. [Chemical formula 12]

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

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene group is included. Preferably, it is more preferable to include a polyalkyleneoxy group. Moreover, it ^{is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferred. Specific examples of the polymerizable group include groups having ethylenically unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetanyl, benzo Azazole group, blocked isocyanate group, methylol group, amino group. As the radical polymerizable group possessed by the polyimide precursor, etc., a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (methyl)allyl group, a group represented by the following formula (III), and the like.

[Chemical formula 13]

In the formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is more preferable. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbons, -CH ₂ CH(OH)CH ₂ -or a polyoxyalkylene group having 4 to 30 carbons. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Alkylene, octamethylene, dodecamethylene, etc., -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH _2- For better. 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. Examples of the monovalent organic group include aromatic groups and aralkyl groups having an acid group bonded to one, two, or three (preferably one) carbons constituting the aryl group. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably an OH group. R ¹¹³ or R ¹¹⁴ is preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1-30. The alkyl group may be any one of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and decyl groups. Tetraalkyl, octadecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl 2-(2-(2-methoxy Ethoxy) ethoxy) ethoxy, 2-(2-(2-ethoxyethoxy) ethoxy) ethoxy) ethoxy, 2-(2-(2-(2- Methoxyethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. 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. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Diacyl, dicyclohexyl and pinenyl (pinenyl). Among them, from the viewpoint of achieving high sensitivity, cyclohexyl is the most preferred. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred. As the aromatic group, specifically, substituted or unsubstituted benzene ring, naphthalene ring, pentene ring, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentabenzene ring, Acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, terphenylene ring, pyrene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine Rings, pyridine rings, pyrimidine rings, dada rings, indole rings, indole rings, benzofuran rings, benzothiophene rings, isobenzofuran rings, quinoline rings, quinoline rings, and quinoline rings , Naphthyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiaxanthene ring, chromene ring, star ring, phenanthrene ring㗁 Thio ring, phenothi ring or brown 𠯤 ring. The benzene ring is the best.

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

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

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

式（2-A）中，A¹ 及A² 表示氧原子，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一個為包含聚合性基團之基團，兩者均為包含聚合性基團之基團為較佳。The repeating unit represented by formula (2) is preferably the 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). With this structure, the exposure latitude can be further expanded. Formula (2-A) [Chemical formula 14]

In the 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 represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both of them are groups containing a polymerizable group.

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

The polyimide precursor may include one type of repeating unit represented by formula (2), or may include two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). Moreover, in addition to the repeating unit of the above formula (2), the polyimide precursor may obviously include other types of repeating units.

As an embodiment of the polyimide precursor of the present invention, 50 mol% or more of the total repeating unit, further 70 mol% or more, especially 90 mol% or more, are repeats represented by formula (2). The polyimide precursor of the unit.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is more preferred, 3.2 or less is more preferred, and 3.1 or less is more preferred. To be even more preferable, 3.0 or less is still more preferable, and 2.95 or less is particularly preferable. 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. In addition, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000. From the viewpoint of developability, the molecular weight dispersion of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and even more preferably 2.2 or more. The upper limit of the degree of dispersion of the molecular weight of the polyimide precursor is not particularly limited. For example, it is preferably 7.0 or less, more preferably 6.5 or less, and more preferably 6.0 or less. In this specification, the degree of molecular weight dispersion is a value calculated from weight average molecular weight/number average molecular weight.

〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as the main component. In this specification, alkali-soluble polyimide means that 0.1 g or more of polyimide is dissolved in 100 g of 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, 0.5 g is dissolved The above polyimine is preferable, and it is more preferable to dissolve 1.0 g or more of polyimine. The upper limit of the above-mentioned dissolution amount is not particularly limited, but 100 g or less is preferable. In addition, from the viewpoint of the film strength and insulating properties of the cured film obtained, the polyimide is preferably a polyimide having a plurality of imine structures in the main chain. In this specification, the "main chain" means the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the "side chain" means the other bonding chain.

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

-Silicon atom- From the viewpoint of the film strength of the cured film obtained, it is preferable that the polyimide has a silicon atom. R silicon atom such as contained in the repeating unit represented by the formula (4) described later of the ¹³¹ is preferred as the organic modified later after the (poly) silicon oxide having a structure comprising repeating units described the following represented by the formula (4) of R ¹³¹ is more preferable. In addition, the above-mentioned silicon atom or the above-mentioned organically modified (poly)siloxane structure may be included in the side chain of the polyimide, but it is preferably included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01-5 mol/g, more preferably 0.05-1 mol/g.

-Ethylene unsaturated bond- From the viewpoint of the film strength of the cured film to be obtained, it is preferable that the polyimide has an ethylenic unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain, or may have an ethylenically unsaturated bond in the side chain, and preferably has an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. It is preferable that the ethylenically unsaturated bond is contained in R ^{132 in the repeating unit represented by formula (4) described later or R 131} in the repeating unit represented by formula (4) described later, as the one having ethylenically unsaturated bond It is more preferable that the group is contained in R ^{132 in the repeating unit represented by formula (4) mentioned later or R 131} in the repeating unit represented by formula (4) mentioned later. Among these, ethylenic unsaturated bond comprises a repeating unit represented by the above formula of the following (4) of the R ¹³¹ is preferred, a group having an ethylenically unsaturated bond to include the following described by the formula (4) ^{R 131} in the repeating unit shown is more preferable. Examples of groups having ethylenically unsaturated bonds include groups such as vinyl groups, allyl groups, and vinyl phenyl groups that have a vinyl group that may be directly bonded to an aromatic ring, and (meth)acrylic acid groups. An amino group, a (meth)acryloxy group, a group represented by the following formula (III), and the like.

[Chemical formula 15]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is more preferable.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH -. (Poly)oxyalkylenes with 2-30 carbons (the carbon number of the alkylenes is preferably 2-12, more preferably 2-6, particularly preferably 2 or 3; repeating number is 1-12 Is preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred) or a combination of two or more groups. In addition, (poly)oxyalkylene means oxyalkylene or polyoxyalkylene.

在式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）氧伸烷基或將該等鍵結2個以上之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（III）中的R²⁰¹ 所鍵結之氧原子的鍵結部位。 在式（R1）～（R3）中，L中的碳數2～12的伸烷基或碳數2～30的（聚）氧伸烷基的較佳態樣與上述R²⁰¹ 中的碳數2～12的伸烷基或碳數2～30的（聚）氧伸烷基的較佳態樣相同。 在式（R1）中，X係氧原子為較佳。 在式（R1）～（R3）中，*的含義與式（III）中的*相同，較佳態樣亦相同。 由式（R1）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有異氰酸基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸基乙酯等）進行反應來獲得。 由式（R2）表示之結構例如可藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥基乙酯等）進行反應來獲得。 由式（R3）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸環氧丙酯等）進行反應來獲得。Among these, R ²⁰¹ is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1). [Chemical formula 16]

In the formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbons, a (poly)oxyalkylene group having 2 to 30 carbons, or a group bonding these two or more X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with an oxygen atom bonded to ^{R 201 in formula (III).} In the formulas (R1) to (R3), the preferred aspect of the alkylene having 2 to 12 carbons or the (poly)oxyalkylene having 2 to 30 carbons in L is the same as the number of carbons in the ^{above R 201} The preferred aspects of the 2-12 alkylene group or the (poly)oxyalkylene group having 2-30 carbon atoms are the same. In the formula (R1), the X-based oxygen atom is preferred. In formulas (R1) to (R3), * has the same meaning as * in formula (III), and preferred aspects are also the same. The structure represented by the formula (R1) can be obtained, for example, by making a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, methacrylic acid 2-isocyanate group) Ethyl ester, etc.) to be obtained by reaction. The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) can be formed by, for example, polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) It is obtained by reaction.

In the formula (III), * represents the bonding site with other structures, and the bonding site with the main chain of the polyimide is preferred.

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

-Crosslinkable group other than ethylenic unsaturated bond- Polyimide may have a crosslinkable group other than ethylenic unsaturated bond. 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 hydroxymethyl groups. R crosslinkable groups other than an ethylenically unsaturated bond, for example, contained in the repeating unit represented by the sum of the later-described formula (4) ¹³¹ is preferred. The amount of crosslinkable groups other than the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.05-10 mol/g, more preferably 0.1-5 mol/g.

-Acid value- When polyimide is used for alkali development, from the viewpoint of improving the developability, 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. good. In addition, 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. In addition, when polyimide is used in development (for example, "solvent development" described below) using a developer with an organic solvent as the main component, the acid value of the polyimide is preferably 2 to 35 mgKOH/g. 3-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is still more preferable. The above-mentioned acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. In addition, as the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0-10 is preferable, and an acid group having a pKa of 3-8 is more preferable. pKa considers the dissociation reaction of hydrogen ions released from oxygen and expresses its equilibrium constant Ka by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, you can refer to the values described in the "Revised 5th Edition Chemistry Handbook Basics" compiled by the Chemical Society of Japan. In addition, when the acid group is a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As the acid group, it is preferable that the polyimide contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and it is more preferable to contain a phenolic hydroxyl group.

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

在式（4）中，R¹³¹ 表示2價有機基團，R¹³² 表示4價有機基團。 具有聚合性基團時，聚合性基團可以位於R¹³¹ 及R¹³² 中的至少一個上，亦可以如下述式（4-1）或式（4-2）所示，位於聚醯亞胺的末端。 式（4-1） [化學式18]

在式（4-1）中，R¹³³ 係聚合性基團，其他基團的含義與式（4）相同。 式（4-2） [化學式19]

R¹³⁴ 及R¹³⁵ 中的至少一個為聚合性基團，不是聚合性基團的情況下為有機基團，其他基團的含義與式（4）相同。The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imine ring, and it preferably contains a repeating unit represented by the following formula (4), including the formula ( 4) Compounds with repeating units and polymerizable groups are more preferred. Formula (4) [Chemical Formula 17]

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 , or it may be located on the polyimide as shown in the following formula (4-1) or formula (4-2) End. Formula (4-1) [Chemical Formula 18]

In the formula (4-1), R ¹³³ is a polymerizable group, and the meaning of the other groups is the same as in the formula (4). Formula (4-2) [Chemical Formula 19]

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 meaning of the other groups is the same as that of formula (4).

The meaning of the polymerizable group is the same as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like mentioned above. R ¹³¹ represents a divalent organic group. ^{As a divalent organic group, the same thing as R 111} in Formula (2) can be illustrated, and a preferable range is also the same. Moreover, as R ¹³¹ , the diamine residue remaining after removal of the amine group of the diamine can be mentioned. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. ^{As a specific example, an example of R 111} in the formula (2) of the polyimide precursor can be given.

When firing from the viewpoint of more effectively suppressing warpage, R ¹³¹ is based diamine residue having preferably at least two of the alkylene glycol units in the main chain. It is more preferable that a total of two or more diamine residues of either or both of the ethylene glycol chain and the propylene glycol chain are contained in one molecule, and it is still more preferable that the diamine residue does not contain an aromatic ring.

Examples of diamines containing one or both of two or more ethylene glycol chains and propylene glycol chains in total include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR- 148, EDR-176, D-200, D-400, D-2000, D-4000 (the above trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy Yl)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but not limited to Such.

R ¹³² represents a tetravalent organic group. ^{As a tetravalent organic group, the same thing as R 115} in Formula (2) can be illustrated, and a preferable range is also the same. For example, ^{the four linkages of the tetravalent organic group exemplified as R 115} are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring. [Chemical formula 20]

In addition, R ¹³² includes a tetracarboxylic acid residue remaining after removing an acid anhydride group from tetracarboxylic dianhydride. ^{As a specific example, an example of R 115} in the formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group on at least one of R ¹³¹ and R ^132. More specifically, as R ¹³¹ , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1)～ (DA-18) As a preferable example, as R ¹³² , the above-mentioned (DAA-1) to (DAA-5) can be cited as more preferable examples.

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

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

In addition, in order to improve the storage stability of the composition, the main chain end of the polyimide is preferably sealed with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochlorine compound, and a monoactive ester compound. Among these, it is more preferable to use monoamines. As preferred compounds for monoamines, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyl Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amine Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-amine Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amine Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenols, etc. Two or more of these may be used, and plural kinds of different terminal groups may be introduced by reacting plural kinds of end-capping agents.

-Imidation rate (closed loop rate)-From the viewpoint of film strength and insulation of the cured film obtained, the imidization rate of polyimide (also referred to as "closed loop rate") is 70% or more More preferably, more than 80% is more preferable, and more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, and it may be 100% or less. For example, the above-mentioned imidization rate can be measured by the following method. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 near ^{1377 cm-1} , which is an absorption peak derived from the imine structure, was determined. Next, after the polyimide was heat-treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 in the vicinity of ^{1377 cm -1 was determined.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be obtained according to the following formula. The imidization rate (%)=(peak intensity P1/peak intensity P2)×100

The polyimide may include all ^{of the repeating units of the above formula (4) containing one type of R 131} or R ¹³² , and may also include the repeating units of the above formula (4) including two or more different types of R ¹³¹ or R ¹³² . Moreover, in addition to the repeating unit of the above formula (4), the polyimide may also include other types of repeating units.

Polyimine can be used, for example, by reacting tetracarboxylic dianhydride with a diamine compound (part of it is substituted into monoamine, that is, a blocking agent) at low temperature, and tetracarboxylic dianhydride (part of being substituted with acid anhydride) at low temperature Or a method of reacting a monochlorine compound or a monoactive ester compound (that is, a blocking agent) with a diamine compound. After the diester is obtained by tetracarboxylic dianhydride and an alcohol, the diamine (substituting a part of the monoamine, that is, blocking A method of reacting in the presence of a terminal agent) and a condensing agent. After obtaining a diester from tetracarboxylic dianhydride and alcohol, chlorination of the remaining dicarboxylic acid and diamine (part of it is substituted with monoamine) The polyimide precursor is obtained by the method of the capping agent), and the polyimide precursor is obtained by using the conventional imidization reaction method, and the complete imidization method is used or the imidization reaction is stopped halfway and introduced Part of the imine structure is synthesized by mixing a fully imidized polymer and its polyimide precursor to introduce a part of the imine structure. As a commercially available product of polyimide, Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation) can be exemplified.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, it is particularly preferred that the weight average molecular weight is 20,000 or more. In addition, when two or more polyimines are contained, the weight average molecular weight of at least one polyimines is preferably within the above-mentioned 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.

在式（3）中，R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團。[Polybenzoxazole Precursor] The polybenzoxazole precursor used in the present invention is not particularly limited in its structure and the like, but preferably contains a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 21]

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.

In formula (3), R ¹²³ and R ^{124 have the same meanings as R 113} in formula (2), and their preferred ranges are also the same. That is, it is preferable that at least one is a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, it is preferable to include at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain 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. As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing linear or branched aliphatic groups (preferably straight-chain) are preferred. A dicarboxylic acid composed of a family group and 2 -COOH is more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2-30, more preferably 2-25, more preferably 3-20, and still more preferably 4-15 , 5～10 are particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. 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, suberic acid, dodecafluoro suberic acid, azela Diacid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid Acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenedioic acid, tricosanedioic acid, twenty-four Alkanedioic acid, pentacosanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonaconanedioic acid, triaconanedioic acid, tridecanedioic acid Acid, tridodecanedioic acid, diethylene glycol acid, and dicarboxylic acid represented by the following formula.

（式中，Z係碳數1～6的烴基，n係1～6的整數。）[Chemical formula 22]

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

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

式中，A表示選自包括-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之群組中之2價基團。[Chemical formula 23]

In the formula, A represents selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -and -C(CH ₃ ) ₂ -The divalent group in the group.

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

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the meaning is the ^{same as R 115} in the above formula (2), and the preferred range is also the same. In addition, R ¹²² is preferably a group derived from a diaminophenol derivative. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4 '-Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 4 ,4'-Diamino-3,3'-dihydroxydiphenyl sulfide, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyl Phenyl) propane, 2,2-bis-(3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl) hexafluoropropane, double -(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-di Hydroxybenzophenone, 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, etc. These diaminophenol screenshots are used alone or in combination.

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

式中，X₁ 表示-O-、-S-、-C（CF₃ ）₂ -、-CH₂ -、-SO₂ -、-NHCO-。[Chemical formula 24]

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

[Chemical formula 25]

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

（在式（A-sc）中，*表示鍵結於由上述式（A-s）表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環。）[Chemical formula 26]

(In the formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the diaminophenol derivative represented by the above formula (As).)

It is believed that in the above formula (As), the ortho position of the phenolic hydroxyl group, that is, the _{substituent at R 3} will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer. It is particularly preferable from the viewpoint of further improving the effect of the high cyclization rate.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, it can maintain high transparency to i-rays and has the effect of having a high cyclization rate when hardened at a low temperature, so it is preferable .

In addition, in the above formula (As), R ₁ is an alkylene group or substituted alkylene group more preferably. Specific examples of the alkylene and substituted alkylenes related to R _{1 include -CH 2} -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) (CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -CH (CH (CH ₃ ) ₂ ) -, -C (CH ₃ ) (CH (CH ₃ ) ₂ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ) -, -CH (CH ₂ CH (CH ₃ ) ₂ ) -, -C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )- etc., among them, it is possible to maintain high transparency to i-rays and high cyclization when hardened at low temperature From the viewpoint of a polybenzoxazole precursor that has an excellent balance of solvent efficiency and sufficient solubility in solvents, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -are Better.

As a method for producing the diaminophenol derivative represented by the above formula (As), for example, refer to paragraphs 0085 to 0094 of JP 2013-256506 A and Example 1 (paragraphs 0189 to 0190). Included in this manual.

As a specific example of the structure of the diaminophenol derivative represented by the above-mentioned formula (A-s), the contents described in paragraphs 0070 to 0080 of JP 2013-256506 A are included, and these contents are incorporated in this specification. Of course, it is not limited to this.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also include other types of repeating structural units. From the viewpoint of being able to suppress warpage accompanying ring closure, it is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

在式（SL）中，Z具有a結構和b結構，R^1s 係氫原子或碳數1～10的烴基，R^2s 係碳數1～10的烴基，R^3s 、R^4s 、R^5s 、R^6s 中的至少1個為芳香族基，剩餘部分為氫原子或碳數1～30的有機基團，該等可以相同，亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。關於Z部分的莫耳%，a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。[Chemical formula 27]

In formula (SL), Z has a structure and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group with ^{1 to 10 carbons, R 2s} is a hydrocarbon group with 1 to 10 carbons, R ^3s , R ^4s , R ^5s , R ^{At least one of 6s} is an aromatic group, and the remainder is a hydrogen atom or an organic group with 1 to 30 carbon atoms, and these may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol% of the Z part, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

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

When the diamine residue represented by the formula (SL) is included as another type of repeating structural unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride as the repeating structural unit. As an example of such a tetracarboxylic acid residue, an example of R ¹¹⁵ in the formula (2) can be given.

For example, when used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited. For example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is more preferable, 2.3 or less is more preferable, and 2.2 The following are further preferred.

在式（X）中，R¹³³ 表示2價有機基團，R¹³⁴ 表示4價有機基團。 具有聚合性基團時，聚合性基團可以位於R¹³³ 及R¹³⁴ 中的至少一個上，亦可以如下述式（X-1）或式（X-2）所示，位於聚苯并㗁唑的末端。 式（X-1） [化學式29]

在式（X-1）中，R¹³⁵ 及R¹³⁶ 中的至少一個為聚合性基團，不是聚合性基團時為有機基團，其他基團的含義與式（X）相同。 式（X-2） [化學式30]

在式（X-2）中，R¹³⁷ 係聚合性基團，其他為取代基，其他基團的含義與式（X）相同。[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it has a polymer compound having a benzoxazole ring. The compound represented by the following formula (X) is preferred, which is represented by the following formula The compound represented by (X) and a compound having a polymerizable group are more preferable. [Chemical formula 28]

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 , or may be located on polybenzoxazole as shown in the following formula (X-1) or formula (X-2) The end. Formula (X-1) [Chemical Formula 29]

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 meaning of the other groups is the same as that of formula (X). Formula (X-2) [Chemical formula 30]

In the formula (X-2), ^R137 is a polymerizable group, the others are substituents, and the meanings of the other groups are the same as in the formula (X).

The meaning of the polymerizable group is the same as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like mentioned above.

R ¹³³ represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group can be mentioned. ^{As a specific example, an example of R 121} in the formula (3) of the polybenzoxazole precursor can be given. In addition, the meaning of the preferred example is the same as that of R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. ^{Examples of the tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. In addition, the meaning of the preferred example is the same as that of R ¹²² . For example, ^{the four linkages of the tetravalent organic group exemplified as R 122} are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical formula 31]

The azolization rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. With the azolization rate of 85% or more, the shrinkage of the film based on the closed loop (which occurs when azolization is heated by heating) becomes smaller, and the occurrence of warpage can be more effectively suppressed.

Polybenzoxazole may include all of the repeating structural units of the above formula (X) containing one kind of R ¹³¹ or R ¹³² , and may also include the repeating of the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² unit. Moreover, in addition to the repeating unit of the above formula (X), the polybenzoxazole may also include other types of repeating structural units.

For example, the diaminophenol derivative is reacted with a ^{dicarboxylic acid containing R 133} or a compound selected from the dicarboxylic acid dichloride and dicarboxylic acid derivative of the above-mentioned dicarboxylic acid to obtain a polybenzoxazole precursor In order to obtain polybenzoxazole, the oxazole can be obtained by using the conventional oxazole reaction method. In addition, in the case of dicarboxylic acid, in order to increase the reaction yield, etc., it is also possible to use an active ester type dicarboxylic acid derivative in which 1-hydroxy-1,2,3-benzotriazole and the like are reacted in advance.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain a cured film with excellent mechanical properties, it is particularly preferred that the weight average molecular weight is 20,000 or more. In addition, when two or more polybenzoxazoles are contained, the weight average molecular weight of at least one polybenzoxazole is preferably within the above-mentioned range.

[Manufacturing methods of polyimide precursors, etc.] The polyimide precursor or the like can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with 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 production method of a polyimide precursor, etc., it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified. Polyimine can be cyclized by thermal imidization, chemical imidization (for example, by using a catalyst to promote the cyclization reaction) after synthesizing the polyimine precursor It can also be directly synthesized into polyimide.

-Capping agent- When manufacturing polyimide precursors, etc., in order to further improve storage stability, it is better to seal the ends of the polyimide precursors with a blocking agent such as acid anhydrides, monocarboxylic acids, monochlorine compounds, and monoactive ester compounds. . As the blocking agent, it is more preferable to use monoalcohol, phenol, mercaptan, thiophenol, and monoamine. Preferred compounds of monoalcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloro Primary alcohols such as methanol and furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary butyl alcohol, adamantanol, etc. Grade alcohol and so on. Examples of preferable compounds of phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and the like. Preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-amino Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid , 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and plural kinds of different terminal groups may be introduced by reacting plural kinds of end-capping agents. In addition, when sealing the amine group at the end of the resin, it can be sealed with a compound having a functional group capable of reacting with the amine group. Preferred sealants for amine groups are carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc., more preferably carboxylic acid anhydride and carboxylic acid chloride. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and the like. Also, preferred compounds of the carboxylic acid chloride include acetyl chloride, propylene chloride, propylene chloride, methacrylic acid chloride, neopentyl chloride, cyclohexane methyl chloride, and 2-ethylhexyl chloride. Chlorine, cinnamon chloride, 1-adamantane methyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzyl chloride, etc.

-Solid precipitation- When manufacturing polyimide precursors, etc., a process of precipitation of solids may be included. Specifically, by precipitating the polyimide precursor and the like in the reaction liquid in water and dissolving it in a solvent that can dissolve the polyimide precursor and the like such as tetrahydrofuran, the solid can be precipitated. After that, by drying the polyimide precursor, etc., a powdered polyimine precursor, etc. can be obtained.

〔content〕 The content of the specific resin in the thermosetting photosensitive composition of the present invention relative to the total solid content of the thermosetting photosensitive composition is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more To be more preferable, 50% by mass or more is still more preferable. In addition, the content of the specific resin in the thermosetting photosensitive composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the thermosetting photosensitive composition, more preferably 99% by mass or less, and 98% by mass % Or less is more preferable, 97 mass% or less is still more preferable, and 95 mass% or less is still more preferable. The thermosetting photosensitive composition of the present invention may include only one type of specific resin, or may include two or more types. When two or more are contained, the total amount is preferably in the above-mentioned range.

＜Sensitizer＞ The thermosetting photosensitive composition contains a photosensitizer. As a photosensitizer, it has the following functions (when the thermosetting photosensitive layer is exposed, free radicals are generated, acid is generated, etc., and the solubility of the thermosetting photosensitive layer to the developer is changed along with the above structural change) The compound is not particularly limited, and examples include photopolymerization initiators, photoacid generators, and the like.

〔Photopolymerization initiator〕 Examples of the photopolymerization initiator include photoradical polymerization initiators, photocationic polymerization initiators, and the like, and photoradical polymerization 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 photoradical polymerization initiator and a free radical crosslinking agent described later, radical polymerization is performed, and the exposed portion of the thermally hardened photosensitive layer is insoluble in the developing solution, and a negative pattern can be formed. The radical photopolymerization initiator is not particularly limited, and for example, it can be appropriately selected from known compounds. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that interacts with a light-excited sensitizer and generates active free radicals.

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

As the photoradical polymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron arene complexes, etc. For these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and this content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

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

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

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

As the aminoacetophenone-based initiator, it is also possible to use the compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength matched with a light source of wavelengths such as 365nm or 405nm.

Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, a commercially available product IRGACURE-819 or IRGACURE-TPO (brand name: all made by BASF), Omnirad 819, or Omnirad TPO (all made by IGM Resins) can be used.

As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like can be exemplified.

As the photoradical polymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred.

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

As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one , 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like. In the thermosetting photosensitive composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group represented by >C=N-O-C(=O)- in the molecule.

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japan Special Publication 2012-014052) The photo-radical polymerization initiator described in No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

The oxime compound of the following structure can also be used. [Chemical formula 32]

In addition, an oxime compound having a fluorine atom can be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 -The compound (C-3) described in paragraph 0101 of Bulletin No. 164471, etc.

As the best oxime compound, oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 or oximes with sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl tri ketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and ketone compounds. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

Further preferred photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium Salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one of the compounds is further preferred, it is even more preferred to use a metallocene compound or an oxime compound, and the oxime compound is even more preferred.

In addition, the photoradical polymerization initiator can also use benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-porolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1, alkylanthraquinones, etc. are condensed with aromatic rings. Quinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used.

[Chemical formula 33]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbons, benzene Group or C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl, cyclohexyl, C2-C12 alkenyl group, which is substituted by one or more oxygen atoms And at least one substituted phenyl or biphenyl group in the interrupted C2-C18 alkyl group and C1-C4 alkyl group, R ^I01 is a group represented by formula (II), or is The same groups as ^{R I00 , R I02} to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen atom.

[Chemical formula 34]

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

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

The content of the photoradical polymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content of the thermosetting photosensitive composition of the present invention, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass. The radical photopolymerization initiator may contain only one kind or two or more kinds. When two or more types of radical photopolymerization initiators are contained, the total amount is preferably in the above-mentioned range.

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

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

When a thermal radical polymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the thermosetting photosensitive composition of the present invention, more preferably 0.1-20% by mass, and still more preferably It is 5 to 15% by mass. The thermal radical polymerization initiator may contain only one kind or two or more kinds. When two or more types of thermal radical polymerization initiators are contained, the total of them is preferably in the above-mentioned range.

-Photoacid generator- The thermosetting photosensitive composition of the present invention preferably contains a photoacid generator. By containing a photoacid generator, for example, acid is generated in the exposed part of the thermosetting photosensitive layer, so that the solubility of the developer (for example, an aqueous alkali solution) of the exposed part is increased, and the exposed part can be removed by the developer. Positive relief pattern. In addition, when the thermosetting photosensitive composition contains a photoacid generator and a thermal crosslinking agent described later, for example, it can also be set as a form in which the crosslinking reaction of the thermal crosslinking agent is promoted by the acid generated in the exposed portion , The exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative relief pattern can be obtained.

Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, ionium salts, and the like.

As the quinonediazide compound, quinonediazide sulfonic acid is bonded to a polyhydroxy compound through an ester, quinonediazide sulfonic acid is bonded to a polyamine compound, and quinonediazide is bonded to a polyamine compound. The sulfonic acid of the azide is bonded to the polyhydroxypolyamine compound through at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional groups of the polyhydroxy compounds and polyamine compounds are substituted by quinonediazide.

In the present invention, as the quinonediazide, any of 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl can be preferably used. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-ray region of the mercury lamp, so it is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonate compound extends to the g-ray region of the mercury lamp, so it is suitable for g-ray exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonate compound and a 5-naphthoquinone diazide sulfonate compound according to the wavelength of exposure. In addition, the naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group may be contained in the same molecule, or 4-naphthoquinone diazide sulfonyl ester compound may be contained in the same molecule. Azosulfonate compound and 5-naphthoquinone diazide sulfonate compound.

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

When the photoacid generator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the thermosetting photosensitive composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5-5%. 15% by mass. The photoacid generator may contain only one type, or may contain two or more types. When two or more kinds of photoacid generators are contained, it is preferable that the total thereof is in the above range.

-Hot 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 acid by heat. Examples include onium salts such as sulfonate, ammonium salt, and phosphonium salt, or carboxylate compounds, sulfonate compounds, and phosphoric acid. Ester compounds such as ester compounds.

As the acid generated from the thermal acid generator by heating, sulfonic acid, phosphoric acid, carboxylic acid, etc. can be cited as examples, sulfonic acid is preferred, and aromatic sulfonic acid is 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 40-300°C, more preferably 80-260°C, further preferably 120-220°C, particularly preferably 120-200°C, and most preferably 140-180°C good. When the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule, the peak temperature of the heat generation peak with the lowest temperature is determined as the acid generation temperature. Examples of equipment used when measuring the acid generation temperature include Q2000 (manufactured by TA Instruments). In addition, 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.

As a commercially available product of a preferable thermal acid generator, the SI series of SANSHIN CHEMICAL INDUSTRY CO., LTD., the CPI series manufactured by San-Apro Ltd., and the K-PURE TAG series manufactured by KING Co., Ltd. can be cited. In addition, JP 2003-277353, JP Hei 2-001470, JP Hei 2-255646, JP Hei 3-011044, JP 2003-183313, and JP 2003- Known thermal acid generators described in various publications such as 277352, Japanese Patent Application Publication No. 58-037003, Japanese Patent Application Publication No. 58-198532, etc.

The content of the thermal acid generator is preferably 0.1-30% by mass relative to the total solid content of the thermosetting photosensitive composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15% by mass , 1.0-10% by mass is particularly preferred. The thermal acid generator may contain only one type or two or more types. When two or more thermal acid generators are contained, the total of them is preferably in the above-mentioned range.

＜Surface active agent＞ The thermosetting photosensitive composition of the present invention contains a surfactant. As the surfactant, nonionic surfactants such as silicone surfactants, hydrocarbon surfactants, and fluorine surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc. can be used Among various surfactants, from the viewpoint of the insulation of the cured film, nonionic surfactants are preferred.

In the thermosetting photosensitive composition of the present invention, it is preferable that the content of the surfactant exceeds 0.1% by mass relative to the total mass of the composition. In the above aspect, the thermosetting photosensitive composition of the present invention can include a group selected from the group consisting of a hydrocarbon-based surfactant described later, a surfactant having a fluorine atom described later, and a surfactant having a silicon atom described later At least one of the surfactants. When two or more kinds of surfactants are contained, the total of them is preferably within the above-mentioned range. The lower limit of the above content is more preferably 0.101% by mass or more, and more preferably 0.105% by mass or more. The upper limit of the content is preferably 5% by mass or less, and more preferably 1% by mass or less. By setting it to include a large amount of this surfactant, for example, it is considered that even in the thin portion of the thermosetting photosensitive layer on an uneven substrate, the surface of the thermosetting photosensitive layer is covered by a large amount of surfactant . Therefore, it is considered that the difference between the amount of interfacial active agent existing on the surface of the thermosetting photosensitive layer in the thick part and the thin part of the thermosetting photosensitive layer becomes smaller, and the difference between the surface free energy of the above-mentioned cured film A and the cured film B becomes smaller. The difference becomes smaller. As a result, even when a cured film is formed on an uneven substrate and another layer is further formed on the obtained cured film, it is easy to suppress the occurrence of defects in the other layer.

In addition, in the thermosetting photosensitive composition of the present invention, the content of the surfactant relative to the total mass of the composition is preferably less than 0.005% by mass. In the above aspect, the thermosetting photosensitive composition of the present invention can include a group selected from the group consisting of a hydrocarbon-based surfactant described later, a surfactant having a fluorine atom described later, and a surfactant having a silicon atom described later At least one of the surfactants. When two or more kinds of surfactants are contained, the total of them is preferably within the above-mentioned range. The lower limit of the content is more preferably 0.0001% by mass or more, and more preferably 0.0005% by mass or more. The upper limit of the above content is preferably 0.0045% by mass or less, and more preferably 0.0042% by mass or less. By setting the content of the surfactant to be low, for example, it is considered that regardless of the thin part of the thermosetting photosensitive layer on the uneven substrate, or the thick part, the heat-hardening photosensitive layer is The amount of surfactant that moves on the surface of the layer becomes smaller. Therefore, it is considered that the difference between the amount of interfacial active agent existing on the surface of the thermosetting photosensitive layer in the thick part and the thin part of the thermosetting photosensitive layer becomes smaller, and the difference between the surface free energy of the above-mentioned cured film A and the cured film B becomes smaller. The difference becomes smaller. As a result, even when a cured film is formed on an uneven substrate and another layer is further formed on the obtained cured film, it is easy to suppress the occurrence of defects in the other layer.

The thermosetting photosensitive composition of the present invention preferably contains a surfactant that does not have fluorine atoms and silicon atoms. As a surfactant which does not have a fluorine atom and a silicon atom, the hydrocarbon-based surfactant mentioned later, etc. are mentioned. It is considered that when a surfactant having a fluorine atom or a silicon atom moves to the surface of the thermosetting photosensitive layer, the surface free energy of the cured film is likely to decrease. Therefore, it is considered that by including a surfactant that does not have fluorine atoms and silicon atoms as a surfactant, even in the thick and thin portions of the thermosetting photosensitive layer, the interfacial activity existing on the surface of the thermosetting photosensitive layer is generated. The difference in the dose reduces the difference between the surface free energy of the cured film A and the cured film B. As a result, even when a cured film is formed on an uneven substrate and another layer is further formed on the obtained cured film, it is easy to suppress the occurrence of defects in the other layer.

In the thermosetting photosensitive composition of the present invention, the content of the hydrocarbon-based surfactant in the composition is preferably 50% by mass or more with respect to the total content of the surfactant. In the above aspect, the thermosetting photosensitive composition of the present invention may further include at least one interface activity selected from the group consisting of a surfactant having a fluorine atom described later and a surfactant having a silicon atom described later Agent. The above content is preferably 60% by mass or more, more preferably 70% by mass or more, 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-based surfactants are contained, the total of them is preferably within the above-mentioned range. The hydrocarbon-based surfactant will be described in detail below. It is considered that even if the hydrocarbon-based surfactant moves to the surface of the thermosetting photosensitive layer, it is difficult to reduce the surface free energy of the cured film. Therefore, it is considered that 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-mentioned surfactants, even in the thick and thin portions of the thermosetting photosensitive layer, it is present in the thermosetting The surface active dose of the photosensitive layer is different, and the difference between the surface free energy of the cured film A and the cured film B will also be reduced. As a result, even when a cured film is formed on an uneven substrate and another layer is further formed on the obtained cured film, it is easy to suppress the occurrence of defects in the other layer.

〔Hydrocarbon Surfactant〕 As the hydrocarbon-based surfactant, it is sufficient that the hydrophobic part is a hydrocarbon-based surfactant, and examples thereof include acetylene-based surfactants, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene hard Polyoxyethylene alkyl ethers such as aliphatic ether, or esters such as phosphoric acid esters, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl esters such as ethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleic acid Esters, sorbitan sesquioleate, sorbitan trioleate and other sorbitan alkyl esters, glycerol monostearate, glycerol monooleate and other monoglyceride alkyl esters , Non-ionic surfactants such as polynuclear phenol ethoxylates; Alkylbenzene sulfonates such as sodium dodecyl benzene sulfonate, sodium butyl naphthalene sulfonate, sodium amyl naphthalene sulfonate, sodium hexyl naphthalene sulfonate, sodium octyl naphthalene sulfonate and other alkyl naphthalene sulfonates Anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium lauryl sulfonate, and sulfosuccinate salts such as sodium dilauryl sulfosuccinate ； Cationic surfactants such as quaternary ammonium salt type alkyl cations; Amphoteric surfactants such as alkyl betaines such as lauryl betaine and stearyl betaine, but are not limited to these.

-Acetylene-based surfactants- The number of ethynyl groups in the molecule in the acetylene-based surfactant is not particularly limited. 1-10 is preferred, 1-5 is more preferred, 1-3 is more preferred, and 1-2 is even more preferred .

The molecular weight of the acetylene-based surfactant is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. There is no particular lower limit, but 200 or more is preferable.

式中，R⁹¹ 及R⁹² 分別獨立地為碳數3～15的烷基、碳數6～15的芳香族烴基或碳數4～15的芳香族雜環基。芳香族雜環基的碳數為1～12為較佳，2～6為更佳，2～4為進一步較佳。 芳香族雜環為5員環或6員環為較佳。芳香族雜環所包含之雜原子係氮原子、氧原子或硫原子為較佳。 R⁹¹ 及R⁹² 可以分別獨立地具有取代基，作為取代基，可舉出下述取代基T。<<The compound represented by the formula (9)>> The acetylene-based surfactant is preferably a compound represented by the following formula (9). [Chemical formula 35]

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

As the substituent T, an alkyl group (the carbon number is preferably 1 to 24, 1 to 12 is more preferable, and 1 to 6 is more preferable), and an arylalkyl group (the carbon number is preferably 7 to 21, 7-15 is more preferred, 7-11 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), alkynyl (carbon number is 2 ~12 is preferred, 2~6 is more preferred, 2~3 is more preferred), hydroxyl group, amino group (carbon number 0~24 is preferred, 0~12 is more preferred, 0~6 is more preferred) ), thiol group, carboxyl group, aryl group (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is more preferred), alkoxy group (carbon number 1-12 is preferred, 1 ～6 is more preferable, 1-3 is more preferable), aryloxy group (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), acyl group (carbon number is 2 ~12 is preferred, 2~6 is more preferred, 2~3 is more preferred), acyloxy group (carbon number 2~12 is preferred, 2~6 is more preferred, 2~3 is further preferred) , Aryl group (the carbon number is preferably 7-23, 7-19 is more preferable, and 7-11 is more preferable), aryloxy group (the carbon number is 7-23 is preferable, and 7-19 is more preferable , 7-11 is more preferred), carbamethanyl (carbon number 1-12 is preferred, 1-6 is more preferred, 1-3 is further preferred), sulfamoyl (carbon number 0-12 Is preferred, 0-6 is more preferred, 0-3 is further preferred), sulfo group, alkylsulfonyl (carbon number 1-12 is preferred, 1-6 is more preferred, 1-3 is further Preferred), arylsulfonyl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is more preferred), heterocyclic group (carbon number 1-12 is preferred, 1~ 8 is more preferred, 2 to 5 are further preferred, and a 5-membered ring or a 6-membered ring is preferred), (meth)acryloyl group, (meth)acryloyloxy group, halogen atom (for example, fluorine atom) , Chlorine atom, bromine atom, iodine atom), oxo group (=O), imino group (=NR ^N ), alkylene group (=C(R ^N ) ₂ ), etc. R ^N is a hydrogen atom or an alkyl group (the carbon number is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 3), preferably a hydrogen atom, methyl, ethyl or propyl. The alkyl part, alkenyl part, and alkynyl part contained in each substituent may be chain or cyclic, and may be linear or branched. When the above-mentioned substituent T is a group which may have a substituent, it may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth)acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group. When the substituent can form a salt group such as a carboxyl group or an amino group, the group can form a salt.

<<The compound represented by the formula (91)>> As the compound represented by the formula (9), a compound represented by the following formula (91) is preferable. [Chemical formula 36]

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 of 2 times n9, n10 is an integer of 1 to 6, m10 is an integer of 2 times of n10 , L9 and l10 are each independently a number of 0 or more and 12 or less. R ⁹³ to R ⁹⁶ are hydrocarbyl groups, in which alkyl groups (the carbon number is preferably 1 to 12, more preferably 1 to 6, and 1 to 3 are more preferable), alkenyl (the carbon number is preferably 2 to 12, and 2 ～6 is more preferable, 2～3 are more preferable), alkynyl group (carbon number 2～12 is more preferable, 2-6 is more preferable, 2～3 is more preferable), aryl group (carbon number is 6～ 22 is preferred, 6-18 is more preferred, 6-10 is further preferred), arylalkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-11 is further preferred) For better. The alkyl group, alkenyl group, and alkynyl group may be linear or cyclic, and may be linear or branched. R ⁹³ to R ⁹⁶ may have a substituent T within the range in which the effects of the present invention are exhibited. In addition, R ⁹³ to R ⁹⁶ may be bonded to each other or form a ring via the linking group L described above. When there are plural substituents T, they may be bonded to each other or may be bonded to the hydrocarbon group in the formula via (or not via) the following linking group L to form a ring. R ⁹³ and R ⁹⁴ are preferably alkyl groups (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are more preferred). Among them, methyl is preferred. R ⁹⁵ and R ⁹⁶ are alkyl groups (1-12 carbon atoms are preferred, 2-6 are more preferred, and 3-6 are more preferred) are preferred. Among them, -(C _n11 R ⁹⁸ _m11 )-R ⁹⁷ is preferred. In particular, R ⁹⁵ and R ⁹⁶ are preferably isobutyl groups. n11 is an integer of 1 to 6, and an integer of 1 to 3 is preferred. m11 is twice the number of n11. R ⁹⁷ and R ⁹⁸ are each independently a hydrogen atom or an alkyl group (the carbon number is preferably from 1 to 12, preferably from 1 to 6 and more preferably from 1 to 3). n9 is an integer of 1 to 6, and an integer of 1 to 3 is preferred. m9 is an integer that is twice n9. n10 is an integer of 1 to 6, and an integer of 1 to 3 is preferred. m10 is an integer that is twice n10. l9 and l10 are each independently a number from 0 to 12. Among them, l9+l10 is preferably a number from 0 to 12, a number from 0 to 8 is more preferred, a number from 0 to 6 is even more preferred, a number greater than 0 and less than 6 is even more preferred, greater than 0 and 3 The following numbers are more preferable. In addition, with regard to l9 and l10, the compound of formula (91) may be a mixture of compounds having different numbers. In this case, the numbers of l9 and l10 or l9+l10 may be numbers including the decimal point or less.

R⁹³ 、R⁹⁴ 、R⁹⁷ ～R¹⁰⁰ 分別獨立地為碳數1～24的烴基，l11及l12分別獨立地為0以上且12以下的數。 其中，R⁹³ 、R⁹⁴ 、R⁹⁷ ～R¹⁰⁰ 係烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、炔基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）為較佳。烷基、烯基、炔基可以為鏈狀或環狀，可以為直鏈或支鏈。R⁹³ 、R⁹⁴ 、R⁹⁷ ～R¹⁰⁰ 可以在發揮本發明的效果之範圍內具有取代基T。又，R⁹³ 、R⁹⁴ 、R⁹⁷ ～R¹⁰⁰ 可以相互鍵結或經由連結基L而形成環。取代基T存在複數個時，可以相互鍵結或者經由（或不經由）連結基L，與式中的烴基鍵結而形成環。 R⁹³ 、R⁹⁴ 、R⁹⁷ ～R¹⁰⁰ 分別獨立地為烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）為較佳。其中，甲基為較佳。 l11+l12為0～12的數為較佳，0～8的數為更佳，0～6的數為進一步較佳，大於0且小於6的數為進一步較佳，大於0且5以下的數為更進一步較佳，大於0且4以下的數為再進一步較佳，可以為大於0且3以下的數，亦可以為大於0且1以下的數。此外，關於l11、l12，式（92）的化合物有時會成為其數不同的化合物的混合物，此時，l11及l12的數或l11+l12可以為包括小數點以下之數。<<The compound represented by the formula (92)>> The compound represented by the formula (91) is preferably a compound represented by the following formula (92). [Chemical formula 37]

R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and 11 and 11 are each independently a number of 0 or more and 12 or less. Among them, R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are alkyl groups (the carbon number is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is more preferable), alkenyl (carbon number 2 to 12 Is preferred, 2-6 is more preferred, 2~3 is more preferred), alkynyl (the carbon number is 2~12 is preferred, 2~6 is more preferred, 2~3 is further preferred), aryl (C6-22 is preferred, 6-18 is more preferred, 6-10 is more preferred), arylalkyl (C7-23 is preferred, 7-19 is more preferred, 7-11 is more preferred) To be further preferred) is preferred. The alkyl group, alkenyl group, and alkynyl group may be chain or cyclic, and may be linear or branched. R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ may have a substituent T within the range in which the effects of the present invention are exhibited. In addition, R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ may be bonded to each other or via the linking group L to form a ring. When there are plural substituents T, they may be bonded to each other or may be bonded to the hydrocarbon group in the formula via (or not via) the linking group L to form a ring. R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are each independently an alkyl group (the carbon number is preferably from 1 to 12, from 1 to 6 is more preferably, and from 1 to 3 is more preferably) is preferably. Among them, methyl is preferred. l11+l12 is preferably a number from 0 to 12, a number from 0 to 8 is more preferred, a number from 0 to 6 is more preferred, a number greater than 0 and less than 6 is even more preferred, and a number greater than 0 and less than 5 The number is more preferable, and a number greater than 0 and less than 4 is even more preferable, and it may be a number greater than 0 and 3 or less, or a number greater than 0 and 1 or less. In addition, with regard to 11 and 11, the compound of formula (92) may be a mixture of compounds having different numbers. In this case, the numbers of 11 and 11 or 11+l12 may be numbers including the decimal point or less.

Examples of acetylene-based surfactants include Surfynol 104 series (trade name, Nissin Chemical Industry CO., Ltd.), Acetyrenol E00, Acetyrenol E40, Acetyrenol E13T, and Acetyrenol 60 (all are trade names, Kawaken Fine Chemicals Co., Ltd.), of which Surfynol 104 series, Acetyrenol E00, Acetyrenol E40, Acetyrenol E13T are preferred, and Acetyrenol E40 and Acetyrenol E13T are more preferred. In addition, Surfynol 104 series and Acetyrenol E00 are surfactants with the same structure.

In addition, as the hydrocarbon-based surfactant, commercially available products can be used. Examples of the commercially available products include ADEKA TOL LB, LA, OA, TN, TO, UA, LO, SO, SP, PC, ADEKA NOL NK, AP , ADEKA ESTOL OEG, TL, S, T, ADEKA SOL CO, COA, ADEKA HOPE MS, YES, TR, ADEKA COL TS, CS, PS, EC, ADEKA MINE 4MAC, 4DAC, MT, ADEKA AMPHOTE PB, AB and other series (All manufactured by ADEKA CORPORATION) etc., but not limited to this.

〔Surface active agent with fluorine atom〕 As the surfactant having a fluorine atom, for example, a surfactant having a fluorocarbon chain and the like can be cited. Specifically, KITAMURA CHEMICALS CO., LTD.'s PF series, DIC Corporation's "MEGAFACE (registered trademark)" series, Sumitomo 3M Limited's FLUORAD series, AGC Inc.'s "Surflon (registered trademark)" series, "AsahiGuard ( Registered trademark)" series, Mitsubishi Materials Electronic Chemicals Co., Ltd.'s EF series, Omnova Solutions Inc.'s Poly-Fox series, etc., but not limited to this.

〔Surface active agent with silicon atom〕 As surfactants having silicon atoms (also referred to as "silicone-based surfactants"), for example, surfactants having polysiloxane chains that can be modified, etc. can be cited. Specifically, examples of silicone-based surfactants include DuPont Toray Specialty Materials Kabushiki Kaisha's SH series, SD series, ST series, BYK-Chemie GmbH's "BYK" series, Shin-Etsu Chemical Co., Ltd. KP series, KF series, NOF CORPORATION’s DISFOAM series, Toshiba Silicones Co., Ltd.’s TSF series, etc., but not limited to this.

〔Other surfactants〕 The thermosetting photosensitive composition of the present invention may contain other surfactants as surfactants. Examples of other surfactants include acrylic/methacrylic resin-based surfactants such as the POLYFLOW series of KYOEISHA CHEMICAL Co., Ltd., and the "DISPARLON (registered trademark)" series of Kusumoto Chemicals, Ltd., but are not limited Here.

＜Solvent＞ The thermosetting photosensitive composition of the present invention contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfenes, amines, and alcohols.

As esters, for example, preferred ones include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. , Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example, alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate ( For example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate Ester and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, Ethyl Caproate , Ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetic acid. Ester, 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 ethyl Ester, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. are preferable.

The ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucanone, and dihydrolevorotone. Glucanone and the like are preferable.

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

As the sulfenite, for example, dimethyl sulfenite is preferable.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Amine, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. The best.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether Base ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-pentanol , Methyl pentanol and diacetone alcohol, etc.

Regarding the solvent, from the viewpoint of improvement of the properties of the coating surface, etc., a form in which two or more types are mixed is also preferable.

In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, acetic acid Butyl ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl card One solvent or a mixed solvent composed of two or more of the alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the thermosetting photosensitive composition of the present invention is preferably 5 to 80% by mass, and it is preferably 5 to 75% by mass. The amount is more preferable, and it is more preferable to set it as 10-70 mass %, it is more preferable to set it as 20-70 mass %, and it is still more preferable to set it as 40-70 mass %. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them is preferably in the above range.

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

The radical crosslinking agent may be a compound having one or more ethylenic unsaturated bonds, and a compound having two or more is more preferable. The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above-mentioned ethylenically unsaturated bond. Furthermore, from the viewpoint of the film strength of the cured film obtained, the thermosetting photosensitive composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical crosslinking agent. As a compound having 3 or more of the above-mentioned ethylenically unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is preferred, and a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, with 3 to 15 ethylenic unsaturated bonds being more preferred. Compounds with 6 ethylenically unsaturated bonds are more preferred. In addition, the compound having 3 or more of the above-mentioned ethylenic unsaturated bonds is preferably a compound having 3 or more of the groups containing the above-mentioned ethylenic unsaturated bond, and a compound having 3 to 15 is more preferred, with 3 to 15 10 compounds are more preferred, and compounds with 3 to 6 are particularly preferred. In addition, from the viewpoint of the film strength of the cured film obtained, the thermosetting photosensitive composition of the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds For better. On the other hand, from the viewpoint of developability, the radical crosslinking agent is particularly preferably a compound having two of the above-mentioned ethylenically unsaturated bonds.

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

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, The amines are preferably esters of unsaturated carboxylic acids and polyol compounds and amines of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, an addition reaction product of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and further having halogen groups Or a substitution reaction product of unsaturated carboxylic acid esters or amides with detachable substituents such as toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, the description in paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated in this specification.

Furthermore, it is also preferable that the radical crosslinking agent is a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl erythritol tri (Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) Base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohol Compounds in which ethylene oxide or propylene oxide is added and then (meth)acrylated, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Application Publication No. 51-037193, etc. The (meth)acrylic urethanes described in the gazette, the polyester acrylates described in the respective gazettes of JP Sho 48-064183, JP Sho 49-043191, and JP Sho 52-030490, Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. Moreover, the polyfunctional (meth)acrylate etc. which are obtained by making the compound which has a cyclic ether group and ethylenically unsaturated bond, such as a polyfunctional carboxylic acid and glycidyl (meth)acrylate react, are mentioned.

In addition, as a preferable radical crosslinking agent other than the above, it is also possible to use the cirrhotic ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. A compound or cardo resin having two or more groups with ethylenically unsaturated bonds.

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

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

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as a radical crosslinking agent. This compound is added to a polyfunctional alcohol A compound formed by (meth)acrylate esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a radical crosslinking agent, and these contents are incorporated in this specification.

As a free radical crosslinking agent, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dineopentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As a commercially available product of a radical crosslinking agent, for example, SR-494 manufactured by Sartomer Company, Inc. is a 4-functional acrylate having 4 ethoxy chains, and SR-494 is a product with 4 ethyleneoxy chains. 2-functional methyl acrylate made by Sartomer Company, Inc. SR-209, 231, 239, made by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxyl chains, as DPCA-60, as having 3 TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, three functional acrylates with a single isobutoxy chain NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA -306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a free radical crosslinking agent, for example, the carbamate described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Publication No. 02-016765 Acrylic acid esters, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have ethylene oxide based Carbamate compounds of the backbone are also preferred. Furthermore, as the radical crosslinking agent, it is also possible to use the structure described in JP-A 63-277653, JP-A 63-260909, and JP-A 01-105238 that have an amine group in the molecule. Or compounds of sulfide structure.

The free radical crosslinking agent may be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphoric acid groups. Among the radical crosslinking agents with acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The unreacted hydroxyl groups of the aliphatic polyhydroxy compounds are reacted with non-aromatic carboxylic acid anhydrides to form an acid group. The free radical crosslinking agent is more preferable. Particularly preferably, the unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with the non-aromatic carboxylic anhydride to have an acid group. Among the free radical crosslinking agents, the aliphatic polyhydroxy compound is one of neopentaerythritol or dineopentaerythritol. Compound. As a commercially available product, for example, M-510, M-520, etc. are mentioned as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd..

The preferred acid value of the free radical crosslinking agent with an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and the developability is also excellent. In addition, the polymerizability is good. /On the other hand, from the viewpoint of the development speed during alkali development, the radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. /The above acid value was measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of the resolution of the pattern and the stretchability of the film, the thermosetting photosensitive composition of the present invention preferably uses a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate (polyethylene glycol dimethacrylate) can be used. Glycol diacrylate and polyethylene glycol chain formula weight is about 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polytetrafluoroethylene Ethylene 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 of bisphenol A (Ethylene oxide) adduct diacrylate, EO adduct of bisphenol A dimethacrylate, PO adduct of bisphenol A diacrylate, EO adduct of bisphenol A dimethyl Acrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, others with urethane A bifunctional acrylate with a bond, and a bifunctional methacrylate with a urethane bond. These can be used by mixing two or more types as needed. Moreover, as a radical crosslinking agent more than bifunctional, diallyl phthalate, triallyl trimellitate, etc. are mentioned. From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As a monofunctional free radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid Allyl compounds such as allyl esters, etc. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

When a radical crosslinking 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. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.

The radical crosslinking agent may be used singly or as a mixture of two or more. When two or more types are used at the same time, the total amount is preferably in the above range.

＜Thermal crosslinking agent＞ The thermosetting photosensitive composition of the present invention preferably contains a thermal crosslinking agent. As a thermal crosslinking agent, as long as it is a compound that has a plurality of groups in the molecule that form a covalent bond with other compounds in the composition or its reaction products, the reaction is promoted by the action of an acid, and it is not It is not particularly limited, and a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl is preferred, and it has a compound selected from the group consisting of hydroxymethyl and alkoxymethyl. A compound having a structure in which at least one group is directly bonded to a nitrogen atom is more preferred. As the thermal crosslinking agent, the following compounds can be mentioned, for example, having melamine, acetylene carbamide, urea, alkylene urea, benzoguanamine and other amine group-containing compounds reacting with formaldehyde or reacting formaldehyde with alcohol and using methylol A compound in which the hydrogen atom of the above-mentioned amino group is substituted by a group or an alkoxymethyl group. The method for producing these compounds is not particularly limited, as long as they have the same structure as the compound produced by the above-mentioned method. In addition, it may be an oligomer in which the methylol groups of these compounds are self-condensed with each other. As the above-mentioned amine-containing compound, the thermal crosslinking agent using melamine is called melamine-based crosslinking agent, and the thermal crosslinking agent using acetylene carbamide, urea or alkylene urea is called urea-based crosslinking agent. The thermal crosslinking agent of alkylene urea is called alkylene urea crosslinking agent, and the one that uses benzoguanamine is called benzoguanamine crosslinking agent. Among them, the thermosetting photosensitive composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and it preferably contains at least one compound selected from the group consisting of acetylene urea described later. At least one compound in the group of cross-linking agents and melamine-based cross-linking agents is more preferable.

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

Specific examples of urea-based crosslinking agents include, for example, monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, and monomethoxymethylated acetylene carbamide. Methylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxy Methylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide Alkylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide or tetrabutoxymethylated acetylene carbamide Acetylene carbamide crosslinking agents such as acetylated acetylene carbamide; Urea crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxy Methylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea, etc. Coupling agent, Monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxy Propylene urea such as methylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea Crosslinking agent, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole Pyridone and so on.

As specific examples of the benzoguanamine-based crosslinking agent, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylol Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated Benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it is also possible to preferably use a compound selected from the group consisting of hydroxymethyl and alkoxymethyl A compound in which at least one group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include terephthalic methanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) Methyl) benzophenone, hydroxymethyl hydroxymethyl benzoate, hydroxymethyl benzene, bis(hydroxymethyl) biphenyl, dimethyl bis(hydroxymethyl) biphenyl, bis(methoxymethyl) benzene, double (Methoxymethyl) cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene Tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy- 1,3-terephthalene dimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As the thermal crosslinking agent, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (above, manufactured by ASAHI YUKIZAI CORPORATION), 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 (above, Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, the same below) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX-279, NIKALACMW-100LM, NIKALACMX-750LM (above, manufactured by SANWA CHEMICAL CO., LTD )Wait.

In addition, the thermosetting photosensitive composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzophenone compounds as the thermal crosslinking agent.

[Epoxy compounds (compounds with epoxy groups)] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C, and it is unlikely to cause film shrinkage because it does not undergo a dehydration reaction due to crosslinking. Therefore, containing the epoxy compound is effective in suppressing the low-temperature curing and warpage of the thermosetting photosensitive composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means the number of repeating units of ethylene oxide of 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, and ethylene glycol bicyclic Alkylene glycol type epoxy resins or polyol hydrocarbons such as oxypropyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. Type epoxy resin; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; epoxy-containing silicone such as polymethyl (glycidoxypropyl) silicone, etc., but It is not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered Trademarks) EXA-4850-150, EPICLON (registered trademark) 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, RIKARESIN (registered trademark) BEO-20E (the above product name, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (commodity Name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081 , CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (above trade name, 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 above, manufactured by Nippon Kayaku Co., Ltd.), etc. Among them, from the viewpoints of suppressing warpage and excellent heat resistance, epoxy resins containing polyethylene oxide groups are preferred. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

[Oxetane compounds (compounds with oxetanyl groups)] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, and 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. As a specific example, the ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or in combination. the above.

〔Benzo 㗁 𠯤 compounds (compounds with benzo azole group)〕 The benzoglucan compound is preferred because of the cross-linking reaction derived from the ring-opening addition reaction and does not produce outgassing during hardening, thereby reducing thermal shrinkage and suppressing warpage.

As preferred examples of the benzoglyph compound, Ba-type benzoglyph, Bm-type benzoglyph, Pd-type benzoglyph, Fa-type benzoglyph (the above product name, manufactured by Shikoku Chemicals Corporation) ), polyhydroxystyrene resin benzo 㗁 adduct, novolak type dihydro benzo 㗁 𠯤 compound. These can be used alone, or two or more of them can be mixed.

The content of the thermal crosslinking agent is preferably 0.1-30% by mass relative to the total solid content of the thermosetting photosensitive composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15% by mass , 1.0-10% by mass is particularly preferred. The thermal crosslinking agent may contain only one kind, or may contain two or more kinds. When two or more thermal crosslinking agents are contained, the total of them is preferably within the above-mentioned range.

<Compounds with sulfonamide structure, compounds with thiourea structure> From the viewpoint of improving the adhesion of the obtained cured film to the substrate, the thermosetting photosensitive composition of the present invention further includes a compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure At least one compound is preferred.

在式（S-1）中，R表示氫原子或有機基團，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R係與下述式（S-2）中的R² 相同的基團為較佳。 具有磺醯胺結構之化合物可以為具有2個以上磺醯胺結構之化合物，具有1個以上磺醯胺結構之化合物為較佳。[Compound with sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical formula 38]

In formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * each independently represents a bonding site to another structure. The above-mentioned R system is preferably the same as ^{R 2} in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having more than one sulfonamide structure is preferred.

在式（S-2）中，R¹ 、R² 及R³ 分別獨立地表示氫原子或1價有機基團，R¹ 、R² 及R³ 中的2個以上可以相互鍵結而形成環結構。 R¹ 、R² 及R³ 分別獨立地表示1價有機基團為較佳。 作為R¹ 、R² 及R³ 的例子，可舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基矽基、烷氧基矽基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、或者將該等組合2個以上之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如，可舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如，可舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基矽基，碳數1～10的烷氧基矽基為較佳，碳數1～4的烷氧基矽基為更佳。作為上述烷氧基矽基，可舉出甲氧基矽基、乙氧基矽基、丙氧基矽基及丁氧基矽基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可具有烷基等取代基。作為上述芳基，可舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、二氫哌喃環、四氫哌喃環、三𠯤環等雜環結構去除1個氫原子之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical formula 39]

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 may be bonded to each other to form a ring structure. Preferably, R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aryl group. Ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, or a combination of two or more of these groups, etc. As the above-mentioned 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. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As said cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are mentioned, for example. As the above-mentioned 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. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned 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. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, Heterocyclic structures such as pyridine ring, pyrimidine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, porphyrin ring, dihydropiperan ring, tetrahydropiperan ring, trihydropyran ring and other heterocyclic structures remove 1 hydrogen Groups of atoms, etc.

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 toluenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, Hydroxynaphthyl sulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzene sulfonamide, p-chlorobenzene sulfonamide, toluene sulfonamide, N,N-di Methanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide , N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

在式（T-1）中，R⁴ 及R⁵ 分別獨立地表示氫原子或1價有機基團，R⁴ 及R⁵ 可以鍵結而形成環，R⁴ 可以與*所鍵結之其他結構鍵結而形成環結構，R⁵ 可以與*所鍵結之其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compound with thiourea structure] The thiourea structure is a structure represented by the following formula (T-1). [Chemical formula 40]

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 can be bonded to form a ring, and R ⁴ can be bonded to other structures with * Bonded to form a ring structure, R ⁵ can be bonded to other structures to which * is bonded to form a ring structure, and * independently represents a bonding site with other structures.

Preferably, R ⁴ and R ⁵ are each independently a hydrogen atom. Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, A carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups, etc. As the above-mentioned 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. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As said cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are mentioned, for example. As the above-mentioned 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. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned 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. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, Heterocyclic structures such as pyridine ring, pyrimidine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, porphyrin ring, dihydropiperan ring, tetrahydropiperan ring, trihydropyran ring and other heterocyclic structures remove 1 hydrogen Groups of atoms, etc. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

在式（T-2）中，R⁴ ～R⁷ 分別獨立地表示氫原子或1價有機基團，R⁴ ～R⁷ 中的至少2個可以相互鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical formula 41]

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 may be bonded to each other to form a ring structure.

In formula (T-2), the same as R (T-1) and the meanings of R ⁴ and R ⁵ of the formula ⁴ and R ^5, preferred aspects are also the same. In the formula (T-2), it ^{is preferable that R 6} and R ⁷ are each independently a monovalent organic group. In the formula (T-2), the preferred aspect of the monovalent organic group in ^{R 6} and R ^{7 is the same as that of the monovalent organic group in R 4} and R ⁵ in the formula (T-1) The appearance is the same.

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1- Adamantylthiourea, N-benzylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diiso Propylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylene thiourea (2-imidazoline thione), Carbimazole, 1,3-dimethyl-2-thiohydantoin, etc.

〔content〕 The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the thermosetting photosensitive composition of the present invention is preferably 0.05-10% by mass, and more preferably 0.1-5% by mass Preferably, 0.2 to 3% by mass is more preferable. The thermosetting photosensitive composition of the present invention may include only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or two or more. When only one type is included, the content of the compound is within the above-mentioned range, and when two or more types are included, the total amount of the compound is preferably within the above-mentioned range.

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

The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetra Azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-piperan ring and 6H-piperan ring, tricyclic ring) compounds, with Thiourea and sulfhydryl-based compounds, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011-059656 can be used. The compound described in paragraph 0052 of JP-A-2012-194520, the compound described in paragraphs 0114, 0116, and paragraph 0118 of JP 2012-194520 A, the compound described in paragraph 0166 of International Publication No. 2015/199219, and the like.

As specific examples of migration inhibitors, the following compounds can be given.

[Chemical formula 42]

When the thermosetting photosensitive composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the thermosetting photosensitive composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass. 0.1 to 1.0% by mass is more preferable.

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

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

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, and p-tertiary butylcatechol can be preferably used. , 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4- Methyl-6-tertiary butyl phenol), N-nitrosophenylhydroxylamine trivalent cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, phenothionine, N-nitroso Diphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4 -Methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N- Ethyl-N-sulfopropyl)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, 1 ,3,5-Tris(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H )-Triketone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 1,1-diphenyl-2-picrylhydrazine, dibutyldithioamino group Copper (II) formate, nitrobenzene, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitroso-N-phenylhydroxyamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

[Chemical formula 43]

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 may be, for example, 0.01 to 20.0% by mass. , 0.01 to 5% by mass is preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is still more preferable. Moreover, when the storage stability of the photosensitive resin composition solution is required, the aspect of 0.02 to 15.0 mass% can also be mentioned preferably, and in this case, 0.05 to 10.0 mass% is more preferable.

There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the total of them is in the above-mentioned range.

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

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

[Chemical formula 44]

As other silane coupling agents, for example, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-epoxy Propoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropoxy Propyl propyl triethoxy silane, p-styryl trimethoxy silane, 3-methacryloxy propyl methyl dimethoxy silane, 3-methacryloxy propyl trimethoxy silane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- 2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-isocyanate propyl triethoxy silane, 3-trimethoxysilyl propyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

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

〔Aluminum series adhesive additives〕 As an aluminum-based adhesive agent, for example, tris(acetate ethyl acetate) aluminum, tris(acetacetone) aluminum, ethyl acetate diisopropyl aluminum, and the like can be cited.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it as the above lower limit or more, the adhesiveness of the cured film after the curing process to the metal layer becomes better, and by setting it as the above upper limit value or less, the heat resistance and mechanical properties of the cured film after the curing process become better. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, the total of them is preferably in the above-mentioned range.

＜Other additives＞ The thermosetting photosensitive composition of the present invention can be blended with various additives as needed within the range where the effects of the present invention can be obtained, for example, sensitizers such as N-phenyldiethanolamine, chain transfer agents, higher fatty acid derivatives , Inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are blended, the total blending amount is preferably 3% by 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. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photo-radical polymerization initiator, etc., to produce effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo chemical changes to decompose, and generate free radicals, acids, or bases. Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, benzophenone series, Michelone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series can also be used System, benzylidene system, oxacyanine system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothionine system, pyrrolopyrazole azomethine system, pyrrolopyrazole azomethine system , Phthalocyanine series, benzopiperan series, indigo series and other compounds. For example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2, 6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'- Bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzene allylindanone, p-dimethylamino Benzylene indanone, 2-(p-dimethylaminophenyl biphenyl)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene) benzothiazole, 2-(p-diphenyl) Methylaminophenyl vinylene) isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) ) Acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-di Methylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl- 7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N -P-toluene diethanolamine, N-phenylethanolamine, 4-terminal benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole , 1-Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene) benzoxazole, 2-(p-dimethylaminostyrene) benzo Thiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzyl Aniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc. In addition, as a sensitizer, a sensitizing dye can also be used. For the details of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, which is incorporated into this specification.

When the thermosetting photosensitive composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the thermosetting photosensitive composition of the present invention is preferably 0.01-20% by mass, 0.1-15 Mass% is more preferable, and 0.5-10 mass% is still more preferable. One kind of sensitizer may be used alone, or two or more kinds may be used at the same time.

[Chain transfer agent] The thermosetting photosensitive composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a _{compound group having -SS-, -SO 2} -S-, -NO-, SH, PH, SiH, and GeH in the molecule can be used for RAFT (Reversible Addition Fragmentation Chain Transfer: Reversible Addition Fragmentation Chain Transfer). Addition, fragmentation, chain transfer) polymerization of dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compound with thiocarbonylthio group. These provide hydrogen to low-activity free radicals to generate free radicals, or after oxidation, they can generate free radicals by deprotonation. In particular, thiol compounds can be preferably used.

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

When the thermosetting photosensitive composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the thermosetting photosensitive composition of the present invention. 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is still more preferable. There may be only one type of chain transfer agent, or two or more types. When there are two or more chain transfer agents, it is preferable that the total of them is in the above-mentioned range.

〔Higher fatty acid derivatives〕 In order to prevent the polymerization hindrance caused by oxygen, the thermosetting photosensitive composition of the present invention may be added with higher fatty acid derivatives such as behenic acid or behenic acid amide, and dried after coating. The middle part is on the surface of the thermosetting photosensitive composition.

In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 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 preferably 0.1 to 10% by mass relative to the total solid content of the thermosetting photosensitive composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, it is preferable that the sum total is within the above-mentioned range.

＜Regarding restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture 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 more preferably less than 0.6% by mass.

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

In addition, as a method of reducing the metal impurities accidentally included in the thermosetting photosensitive composition of the present invention, the following method can be cited: as a raw material constituting the thermosetting photosensitive composition of the present invention, selecting a low metal content The raw materials of the thermosetting photosensitive composition of the present invention are filtered by filters, and the inside of the device is lined with polytetrafluoroethylene, etc., and distillation is carried out under the condition of suppressing pollution as much as possible.

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

As the storage container of the thermosetting photosensitive composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into the raw material or thermosetting photosensitive composition, it is better to use a multi-layer bottle with 6 types of 6-layer resins to form the inner wall of the container, and a bottle with 6 types of resins into a 7-layer structure. good. As such a container, for example, the container described in JP 2015-123351 A can be cited.

＜Use of thermosetting photosensitive composition＞ The thermosetting photosensitive composition of the present invention is a composition used to form a thermosetting photosensitive layer, and is more preferably used for forming a thermosetting photosensitive layer based on a slit coating method. The thermosetting photosensitive composition of the present invention is preferably applied to a non-uniform substrate. As a non-uniform substrate, when a thermosetting photosensitive layer is formed on the substrate, the thickness of the thermosetting photosensitive layer may not be a uniform thickness of the substrate. For example, a substrate with a stepped surface, A substrate with an uneven physical shape on the surface of a substrate such as an inclined substrate, or a substrate with uneven chemical properties on the surface of the substrate such as only a part of the surface that is not easily compatible with the composition. A substrate with a step refers to a substrate with a step on the surface, and only a substrate with an uneven surface. A substrate with a slope on the surface refers to a substrate with a slope on at least a part of the surface, and only a substrate with an uneven surface. Examples of substrates with uneven chemical properties on the surface of the substrate such that only part of the surface is not easily compatible with the composition, for example, include a substrate with a different material on the surface of the substrate, and a substrate with a surface treatment on only a part of the surface. The material, etc., even if the surface is flat, as long as it is a substrate on which a thermosetting photosensitive layer of uniform thickness is not formed. Examples of substrates with different materials on part of the surface of the substrate include a case where an insulating layer and conductor wiring are provided on the surface of the substrate. The height difference between the highest part and the lowest part on a substrate with uneven physical shape of the substrate surface (a substrate with uneven surface height) is preferably 5 to 90% relative to the average thickness of the thermosetting photosensitive layer , 10 to 80% is more preferable, and 12 to 60% is still more preferable. The physical shape of the substrate surface is not particularly limited. The surface of the substrate is not particularly limited, and it is rectangular, cube-shaped, cylindrical, hemispherical, cone-shaped, cone-shaped, sloped, ridge-shaped, and valley-shaped. Or a saddle-like shape with a height in the thickness direction or a low shape in the thickness direction may be formed with a height difference in the thickness direction. The above-mentioned height difference may be a difference based on the shape of the substrate, or may be a difference formed by an element formed on the substrate by an electrode, an insulating film, or the like, and it is not limited to which element is formed.

The thermosetting photosensitive composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of 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-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as dust or particles in the thermosetting photosensitive composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. Regarding the filter pore size, for example, it may be 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. The filter can be cleaned in advance with an organic solvent. In the filter filtration process, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering by pressure, the applied pressure 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. It is more preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbent materials. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

(Cured film, laminate, semiconductor device, and manufacturing methods of these) Next, the cured film, the laminated body, the semiconductor device, and the manufacturing method thereof will be described.

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

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. The layered product of the present invention includes two or more cured films, and it is preferable to include a metal layer between any of the above-mentioned cured films. For example, a laminated body including 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 can be cited as a preferable one. The first cured film and the second cured film are both cured films of the present invention. For example, the first cured film and the second cured film are both cured by curing the thermosetting photosensitive composition of the present invention The aspect of the resulting film is the better one. The thermosetting light-sensitive composition of the present invention for forming the above-mentioned first cured film and the thermosetting light-sensitive composition of the present invention for forming the above-mentioned second cured film may be the same composition or may be Compositions of different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), or a case where a pattern is formed by etching an insulating film for actual mounting purposes as described above, etc. can be mentioned. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaki/Supervisor, CMC Technical Library "Polyimide Materials The foundation and development of "Polyimine" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

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

The manufacturing method of the cured film of the present invention (hereinafter also referred to simply as "the manufacturing method of the present invention") preferably includes a film formation process including applying the thermosetting photosensitive composition of the present invention to a substrate to form a film. The method for producing a cured film of the present invention preferably includes the above-mentioned film formation process, an exposure process for exposing the film, and a development process for developing the film. Furthermore, it is more preferable that the method for producing a cured film of the present invention includes a heating process of heating the above-mentioned film. Specifically, the manufacturing process including the following (a) to (d) is also preferable. (A) Film formation process of applying a thermosetting photosensitive composition to a substrate to form a film (thermosetting photosensitive composition layer) (B) Exposure process for exposing the film after the film formation process (C) Development process for developing the exposed film (D) Heating process for heating the developed film By heating in the above heating process, the resin layer hardened by exposure can be further cured. In this heating process, for example, the thermal acid generator described above decomposes, and the generated acid promotes the crosslinking of the thermal crosslinking agent, thereby obtaining sufficient curability.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment follows the above-mentioned manufacturing method of the cured film. After the cured film is formed, the process of (a) or the process of (a) to (c) or the process of (a) to (d) is performed again. Process. In particular, it is preferable to sequentially perform the above-mentioned processes a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By layering the cured film in this way, a layered body can be formed. In the present invention, it is particularly preferable to provide a metal layer on the part where the cured film is provided, between the cured films, or both. In addition, in the production of the laminate, it is not necessary to repeat all the processes of (a) to (d). As described above, it can be performed multiple times at least (a), preferably (a) to (c) or (a) ~(d) Process to obtain a laminate of cured film.

<Film formation process (layer formation process)> The manufacturing method of the preferred embodiment of the present invention includes a film formation process (layer formation process) in which a thermosetting photosensitive composition is applied to a substrate to form a film (layered).

The type of substrate can be appropriately set according to the application. It can be used to make substrates for semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, and reflective films. , Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display panels (PDP), etc., are not particularly limited. In the present invention, in particular, semiconductor manufacturing substrates are preferred, and silicon substrates and mold resin substrates are more preferred. In addition, as the base material, for example, a plate-shaped base material (substrate) is used.

In addition, when the thermosetting photosensitive composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.

As a method of applying the thermosetting photosensitive composition to the substrate, coating is preferred.

Specifically, as applicable methods, there can be exemplified dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, Slit coating method and inkjet method, etc. From the viewpoint of the thickness uniformity of the thermosetting photosensitive composition layer, the spin coating method, the slit coating method, the spraying method, and the inkjet method are more preferable. From the viewpoint of easily obtaining the effects of the present invention, the slit The coating method is preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit Coating method, spraying method, inkjet method, etc. are preferable. When using the spin coating method, for example, it can be applied at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds, and it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. In addition, in order to obtain a uniform film thickness, it is also possible to perform coating in combination with a plurality of rotation speeds. In addition, it is also possible to apply a method of transferring a coating film formed by applying the above-mentioned applying method on a pseudo support in advance to a substrate. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used. .

＜Drying process＞ The manufacturing method of the present invention may further include a drying process to remove the solvent after the film (thermosetting photosensitive composition layer) is formed, and the film formation process (layer formation process) is followed. The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of the solvent of the photosensitive resin composition solution is large, vacuum drying and heat drying can also be combined. A hot plate, a hot-air oven, etc. can be used for the heating and drying, and there is no particular limitation.

<Exposure Process> The manufacturing method of the present invention may include an exposure process for exposing the above-mentioned film (thermosetting photosensitive composition layer). The exposure amount is not particularly limited as long as it can harden the thermosetting photosensitive composition. For example, in terms of exposure energy conversion at a wavelength of 365 nm, 100 to 10,000 mJ/cm ² is preferable, and 200 to 8,000 mJ/cm ² For better.

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

Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc., (7) secondary YAG laser Harmonic 532nm, third harmonic 355nm. For the thermosetting photosensitive composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is preferred. In this way, particularly high exposure sensitivity can be obtained. In addition, from the viewpoints of operability and productivity, a wide (3 wavelengths of g, h, and i rays) light source for a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferable.

＜Development process＞ The manufacturing method of the present invention may include a development process of developing (developing the above-mentioned film) the exposed film (thermosetting photosensitive composition layer). By developing, for example, in the case of a negative photosensitive resin composition, the unexposed part (non-exposed part) can be removed. The development method is not particularly limited as long as the desired pattern can be formed. For example, development methods such as coating, spraying, dipping, and ultrasonic can be used.

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

In alkaline development, as the developer, a developer with an organic solvent content of 10% by mass or less relative to the total mass of the developer is preferred, a developer with 5% by mass or less is more preferred, and a developer with 1% by mass or less To be further preferred, a developer containing no organic solvent is particularly preferred. The developer in alkali development is more preferably an aqueous solution with a pH of 10-15. As the alkali compound contained in the developer in the alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, metasilica Sodium, potassium metasilicate, ammonia or amine, etc. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, and quaternary ammonium hydroxide. , Tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, etc. Among them, metal-free alkali compounds are preferred, and ammonium compounds are more preferred. There may be only one kind of alkali compound, or two or more kinds. When there are two or more kinds of alkali compounds, it is preferable that the total of them is in the above-mentioned range.

In solvent development, it is more preferable that the developer 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, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula from ChemBioDraw (Chemical Biological Diagram).

Regarding organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl Ethyl acid, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate Ester, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid Ethyl ester, etc.)), 3-alkoxypropionic acid alkyl esters (example: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (example: Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and Ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), acetone Methyl acrylate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve 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 as the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be preferably mentioned, and as Cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, etc., and as the sludge, preferably dimethyl Yaqi.

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

In addition, a surfactant may be contained in the developer.

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

After the treatment with the developer, it can be further rinsed. In the case of solvent development, it is better to rinse with an organic solvent different from the developer. For example, propylene glycol monomethyl ether acetate can be mentioned. Preferably, the rinsing time is 5 seconds to 5 minutes. In addition, it is also possible to include a process of using both developer and rinsing solution between development and rinsing. The time of the above process is preferably 1 second to 5 minutes. In the case of alkali development, it is better to rinse with pure water. The rinsing time is preferably 5 seconds to 1 minute.

＜Heating process＞ The manufacturing method of the present invention preferably includes a process of heating the developed film (heating process). It is preferable to include a heating process after the film forming process (layer forming process), drying process, and developing process. In the heating process, for example, cyclization of polyimide precursors or polybenzoxazole precursors, crosslinking of unreacted radical crosslinking agents, crosslinking of unreacted thermal crosslinking agents, etc. can be performed . As the heating temperature (maximum heating temperature) of the layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is even more preferred, 150°C or higher is even more preferred, and 160°C or higher is even further Preferably, 170°C or higher is even more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is more preferred, 250°C or less is even more preferred, and 220°C or less is still more preferred.

From the temperature at the start of heating to the maximum heating temperature, heating is preferably performed at a temperature increase rate of 1-12°C/min, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured film can be alleviated.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at the beginning of the process when heating to the highest heating temperature. For example, when the thermosetting photosensitive composition is applied to a substrate and then dried, the temperature of the dried film (layer) is, for example, 30 to lower than the boiling point of the solvent contained in the thermosetting photosensitive composition. It is preferable that the temperature of 200°C starts to increase gradually.

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

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating at a heating temperature of 180°C to 320°C is preferable, and heating at 180°C to 260°C is more preferable. The reason for this is not certain, but it is thought that by setting the temperature at this temperature, the ethynyl groups of the specific resins between the layers undergo crosslinking reaction with each other.

Heating can be carried out in stages. As an example, a pre-treatment process can be performed at 3°C/min from 25°C to 180°C and holding at 180°C for 60 minutes, and 2°C/min from 180°C to 200°C and holding at 200°C for 120 minutes. As the heating temperature of the pretreatment process, 100-200°C is preferred, 110-190°C is more preferred, and 120-185°C is even more preferred. In this pre-treatment process, as described in the specification of US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. Through this kind of pre-treatment process, the characteristics of the film can be improved. The pre-treatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pre-treatment may be a two-stage or more process, for example, the pre-treatment process 1 may be performed in the range of 100-150°C, and then the pre-treatment process 2 may be performed in the range of 150-200°C.

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

From the viewpoint of preventing decomposition of the specific resin, it is preferable to perform the heating process in a low oxygen concentration environment by performing the heating process under a vacuum in which an inert gas such as nitrogen, helium, and argon flows. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

＜Metal layer forming process＞ The manufacturing method of the present invention preferably includes a metal layer forming process 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 types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is still more preferable.

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited.

As for the thickness of the metal layer, at the thickest part, 0.1-50 μm is preferable, and 1-10 μm is more preferable.

＜Layer Process＞ Preferably, the manufacturing method of the present invention further includes a build-up process.

The build-up process includes on the surface of the cured film (resin layer) or the metal layer, and then sequentially perform one of (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process. A series of manufacturing processes. Among them, it may be a mode in which only the film formation process of (a) is repeated. In addition, it can also be set as (d) a state in which the heating process is performed uniformly at the end or in the middle of the buildup. That is, it can also be set as the following aspect: repeat the process of (a) to (c) a predetermined number of times, and then heat (d) to uniformly harden the laminated thermosetting photosensitive composition layer . In addition, (c) the development process may include (e) the metal layer forming process. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed uniformly after a predetermined number of laminations. There is no doubt that the above-mentioned drying process and heating process can also be appropriately included in the build-up process.

When the build-up process is further performed after the build-up process, the surface activation treatment process may be further performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer formation process. As the surface activation treatment, plasma treatment can be exemplified.

The above-mentioned layering process is preferably carried out 2 to 5 times, and it is more preferable to carry out 3 to 5 times.

For example, resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer are preferably three or more and seven or less resin layers, and more preferably three or more and five or less resin layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the thermosetting photosensitive composition in such a manner that the metal layer is further covered after the metal layer is provided. Specifically, it can be mentioned that (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, (d) heating process are repeated in sequence, or (a) is repeated in sequence Film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process is uniformly set at the end or in the middle. By alternately laminating the thermosetting photosensitive composition layer (resin layer) and the metal layer forming process, the thermosetting photosensitive composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the thermosetting photosensitive composition of the present invention is used to form an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and FIG. 1 Records, these contents are incorporated into this manual. [Example]

Hereinafter, the benzene invention will be described in further detail with examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

<Synthesis Example 1> [PIP-1: Using oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether Synthesis of polyimide precursor PIP-1 of 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate] Mix 10.00g (32.3 millimoles) of oxydiphthalic dianhydride (dried at 140°C for 12 hours) , 9.48g (32.3 millimoles) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (dried at 140°C for 12 hours), 16.8g (129 millimoles) of methyl 2-Hydroxyethyl acrylate, 0.05g hydroquinone, 20.4g (258 millimoles) pyridine, 100g diglyme (diethylene glycol dimethyl ether), and stir at 60°C For 18 hours, the diester of pyromellitic acid and 2-hydroxyethyl methacrylate and the diester of 3,3',4,4'-biphenyltetracarboxylic dianhydride were produced. The reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ , the viscosity increases. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08g (58.7 millimoles) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was maintained at a temperature of -5 to 0°C. Add dropwise to the reaction mixture for 20 minutes. Next, after reacting the solution with the reaction mixture at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine 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. Next, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure, thereby obtaining the polyimide precursor PIP-1.

＜Synthesis example 2＞ [PIP-2: Synthesis of polyimide precursor PIP-2 using oxydiphthalic dianhydride, 4,4’-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] In the synthesis of the polyimide precursor PIP-1, 10.00g (32.3 millimoles) of oxydiphthalic dianhydride and 9.48g (32.3 millimoles) of 3,3',4, 4'-Biphenyltetracarboxylic dianhydride was changed to 20.01g (64.5 millimoles) of oxydiphthalic dianhydride, except for the same as the synthesis of polyimide precursor PIP-1 Methods, the polyimide precursor PIP-2 was synthesized.

＜Synthesis example 3＞ 〔PI-1: Using oxygen diphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,3-bis(3-aminopropyl)tetramethyl Synthesis of polyimide PI-1 based on disiloxane and 2-isocyanatoethyl methacrylate] In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 65.56g (179mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was removed while removing water. ) And 1,3-bis(3-aminopropyl)tetramethyldisiloxane 2.48g (10mmol) are dissolved in 300g of N-methylpyrrolidone (NMP). Next, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40°C for 2 hours. After stirring, nitrogen was flowed at a flow rate of 200 ml/min, the temperature was raised to 180°C, and stirring was carried out for 6 hours. After cooling the above-mentioned reaction liquid to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise to this solution, and after stirring at 25°C for 2 hours, it was 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 at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, rinsed with 1.5 liters of water, and the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again, thereby obtaining polyimide. The obtained polyimide was dried at 40°C for 1 day under reduced pressure, thereby obtaining PI-1.

＜Synthesis example 4＞ 〔PI-2: Using oxydiphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1,3-bis(3-aminopropyl)tetramethyl Synthesis of polyimide PI-2 based on disiloxane] In the synthesis of polyimide PI-1, except that "after cooling the above reaction solution to 25°C, 0.005 g of p-methoxyphenol was added and dissolved, the solution was added dropwise to methacrylic acid 2- 24.82 g (160 mmol) of ethyl isocyanate, stirred at 25°C for 2 hours, and then stirred at 60°C for 3 hours. Cooled to 25°C, added 10 g of acetic acid and stirred at 25°C for 1 hour "Except for this operation, polyimide PI-2 was synthesized by the same method as the synthesis of polyimide PI-1.

＜Synthesis example 5＞ [Synthesis of polybenzoxazole precursor PBP-1 using 4,4'-oxobenzyl 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 stirred and dissolved in 200 g of N-methylpyrrolidone. Next, 12.1 g (153 millimoles) of pyridine was added, and 20.7 g (70.1 millimoles) of 4,4'-oxobenzoyl chloride was added dropwise over 1 hour while maintaining the temperature at -10 to 0°C. Ear) A solution dissolved in 75 g of N-methylpyrrolidone. After stirring for 30 minutes, 1.00 g (12.7 millimoles) of acetyl chloride was added, and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor was collected by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polybenzoxazole precursor PBP-1 was dried at 45°C for 3 days.

＜Synthesis example 6＞ [Synthesis of polybenzoxazole PB-1 using 4,4'-oxobenzyl chloride and 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane] The above-mentioned polybenzoxazole precursor PBP-1 was dissolved in 300 g of N-methylpyrrolidone (NMP), and the temperature was raised to 180° C. while flowing nitrogen at a flow rate of 200 ml/min, followed by stirring for 6 hours. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polybenzoxazole was collected by filtration, rinsed with 1.5 liters of water, and the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again, thereby obtaining polybenzoxazole. The obtained polybenzoxazole was dried at 40°C for 1 day under reduced pressure, thereby obtaining polybenzoxazole PB-1.

<Examples and Comparative Examples> In each example, the components described in the following Table 1, Table 2 or Table 3 were mixed to obtain each thermosetting photosensitive composition. In addition, in each comparative example, the components described in Table 2 below were mixed to obtain each comparative composition. Specifically, the content of the components described in Table 1, Table 2 or Table 3 is the amount described in "Parts by mass" in Table 1, Table 2 or Table 3. In addition, in each composition, the content of the solvent was such that the solid content concentration of the composition became the value described in Table 1, Table 2, or Table 3. The entry in the “metal concentration” column in Table 1, Table 2 or Table 3 indicates 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 column of surfactant means that 0.07 parts by mass of C-1 and 0.03 parts by mass are used The situation of C-3. The obtained thermosetting photosensitive composition and the comparative composition were filtered under pressure through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in Table 1, Table 2, or Table 3, the description of "-" indicates that the composition does not contain the component.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 composition Specific resin species PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PI-1 PIP-2 Mass parts 86 86 86 86 86 86 86 86 86 86 54 84 Free radical crosslinker species B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-2 B-1 Mass parts 6.9 6.9 6.9 6.9 6.9 6.9 6.9 6.9 6.9 6.9 3 10 species - - - - - - - - - - B-3 - Mass parts - - - - - - - - - - 28 - Surfactant species C-1 C-1 C-2 C-2 C-3 C-3 C-3 C-3 /C-1 C-3 /C-1 C-3 /C-1 C-3 C-3 Mass parts 0.25 0.01 0.25 0.01 0.25 0.01 0.1 0.05 /0.05 0.07 /0.03 0.03/0.07 0.1 0.1 Sensitizer species D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-1 Mass parts 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 5 3 Thermal crosslinking agent species - - - - - - - - - - E-1 - Mass parts - - - - - - - - - - 9 - Silane coupling agent species F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-2 F-1 Mass parts 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 1 1.6 species F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 - - Mass parts 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 - - Thermal alkali generator species - - - - - - - - - - - G-1 Mass parts - - - - - - - - - - - 0.6 Polymerization inhibitor species H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-2 H-3 Mass parts 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.02 0.2 additive species I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-2 I-3 Mass parts 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 1 0.3 Solvent species J-1 J-1 J-1 J-1 J-1 J-1 J-1 J-1 J-1 J-1 J-2 J-2 Ratio in solvent 80 80 80 80 80 80 80 80 80 80 80 80 species J-3 J-3 J-3 J-3 J-3 J-3 J-3 J-3 J-3 J-3 J-4 J-4 Ratio in solvent 20 20 20 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 Metal concentration (ppm) 1 1 1 1 1 1 1 1 1 1 1 1 Process Film thickness (μm) 30 30 30 30 30 30 30 30 30 30 30 30 Developer K-1 K-1 K-1 K-1 K-1 K-1 K-1 K-1 K-1 K-1 K-2 K-1 Hardening temperature (℃) 220 220 220 220 220 220 220 220 220 220 220 220 Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation results Absolute value of the difference in surface free energy 2 0 5 1 1 0 1 2 1 4 1 1 Surface free energy of cured film A twenty one 32 25 32 29 32 30 30 31 29 30 30 Absolute value/surface free energy of cured film A 10% 0% 20% 3% 3% 0% 3% 7% 3% 14% 3% 3% Substrate step adaptability A A A A A A A A B B A A Pattern formation B A B A A A A A B B B A

[Table 2] Example Comparative example 13 14 15 16 17 18 19 20 1 2 3 composition Specific resin species PIP-1 PIP-1 PIP-1 PIP-1 PI-2 PIP-1 PBP-1 PB-1 PIP-1 PI-1 PIP-1 Mass parts 86 86 86 86 80 86 86 80 86 54 86 Free radical crosslinker species B-1 B-1 B-1 B-1 - B-1 B-1 - B-1 B-2 B-1 Mass parts 6.9 6.9 6.9 6.9 - 6.9 6.9 - 6.9 3 6.9 species - - - - - - - - - B-3 - Mass parts - - - - - - - - - 28 - Surfactant species C-4 C-5 C-6 C-7 C-3 C-3 C-3 C-3 - - C-1 Mass parts 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - - 0.1 Sensitizer species D-1 D-1 D-1 D-1 D-3 D-1 D-1 D-3 D-1 D-2 D-1 Mass parts 1.7 1.7 1.7 1.7 20 1.7 1.7 20 1.7 5 1.7 Thermal crosslinking agent species - - - - E-1 - - E-1 - E-1 - Mass parts - - - - 9 - - 9 - 9 - Silane coupling agent species F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-2 F-1 F-2 F-1 Mass parts 0.9 0.9 0.9 0.9 1 0.9 0.9 1 0.9 1 0.9 species F-3 F-3 F-3 F-3 - F-3 F-3 - F-3 - F-3 Mass parts 0.9 0.9 0.9 0.9 - 0.9 0.9 - 0.9 - 0.9 Thermal alkali generator species - - - - - - - - - - - Mass parts - - - - - - - - - - - Polymerization inhibitor species H-1 H-1 H-1 H-1 H-2 H-1 H-1 H-2 H-1 H-2 H-1 Mass parts 0.2 0.2 0.2 0.2 0.02 0.2 0.2 0.02 0.2 0.02 0.2 additive species I-1 I-1 I-1 I-1 I-2 I-1 I-1 I-2 I-1 I-2 I-1 Mass parts 3.4 3.4 3.4 3.4 1 3.4 3.4 1 3.4 1 3.4 Solvent species J-1 J-1 J-1 J-1 J-2 J-1 J-1 J-2 J-1 J-2 J-1 Ratio in solvent 80 80 80 80 80 80 80 80 80 80 80 species J-3 J-3 J-3 J-3 J-4 J-3 J-3 J-4 J-3 J-4 J-3 Ratio in solvent 20 20 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 Metal concentration (ppm) 1 1 1 1 1 1 1 1 1 1 1 Process Film thickness (μm) 30 30 30 30 30 20 30 30 30 30 30 Developer K-1 K-1 K-1 K-1 K-2 K-1 K-1 K-2 K-1 K-2 K-1 Hardening temperature (℃) 220 220 220 220 220 220 220 220 220 220 220 Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 Evaluation results Absolute value of the difference in surface free energy 1 1 1 1 1 1 1 1 0 0 7 Surface free energy of cured film A 30 30 30 30 30 30 30 30 32 32 twenty two Absolute value/surface free energy of cured film A 3% 3% 3% 3% 3% 3% 3% 3% 0% 0% 32% Substrate step adaptability A A A A B A A B C C C Pattern formation A A A A B A A B C C B

[table 3] Example twenty one twenty two twenty three twenty four composition Specific resin species PIP-2 PIP-1 PIP-2 PIP-2 Mass parts 82.8 86 82.8 82.4 Free radical crosslinker species B-2 B-1 B-2 B-2 Mass parts 10 6.9 10 10 Surfactant species C-3 C-1 C-3 C-3 Mass parts 0.1 0.4 0.1 0.14 Sensitizer species D-1 D-1 D-1 D-1 Mass parts 3 1.3 3 3 Thermal crosslinking agent species - - - - Mass parts - - - - Silane coupling agent species F-1 F-1 F-1 F-1 Mass parts 1.6 1.8 1.6 1.6 Thermal alkali generator species G-1 - G-1 G-1 Mass parts 2 - 2 2 Polymerization inhibitor species H-3 H-1 H-3 H-3 Mass parts 0.2 0.2 0.2 0.2 additive species I-3 I-1 I-3 I-3 Mass parts 0.3 3.4 0.3 0.3 Solvent species J-2 J-1 J-2 J-2 Ratio in solvent 80 80 80 80 species J-4 J-3 J-4 J-4 Ratio in solvent 20 20 20 20 Solid content concentration 42 27 42 30 Metal concentration (ppm) 1 1 1 1 Process Film thickness (μm) 30 10 20 10 Developer K-1 K-1 K-1 K-1 Hardening temperature (℃) 230 220 230 230 Hardening time (min) 180 120 180 180 Evaluation results Absolute value of the difference in surface free energy 1 2 1 1 Surface free energy of cured film A 30 twenty two 30 30 Absolute value/surface free energy of cured film A 4% 10% 4% 4% Substrate step adaptability A A A A Pattern formation A B A A

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

〔Specific resin〕 ・PIP-1～PIP-2: PIP-1～PIP-2 synthesized in the above ・PI-1～PI-2: PI-1～PI-2 synthesized in the above ・PBP-1: PBP-1 synthesized in the above ・PB-1: PB-1 synthesized in the above

〔Free radical crosslinking agent〕 ・B-1: Tetraethylene glycol dimethacrylate ・B-2: Dineopentaerythritol hexaacrylate ・B-3: LIGHT ESTER BP-6EM (manufactured by KYOEISHA CHEMICAL Co., LTD.)

〔Interface active agent〕 ・C-1: PF-6320 (manufactured by KITAMURA CHEMICALS CO., LTD.) ・C-2: KF-6048 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・C-3: Acetyrenol E00 (manufactured by Kawaken Fine Chemicals Co., Ltd.) ・C-4: ADEKA TOL LA-775 (manufactured by ADEKA CORPORATION) ・C-5: ADEKA ESTOL S-20 (manufactured by ADEKA CORPORATION) ・C-6: ADEKA COL PS-440E (manufactured by ADEKA CORPORATION) ・C-7: ADEKA TOL PC-6 (manufactured by ADEKA CORPORATION)

上述D-3按照國際公開第2017/217292號中記載之合成方法進行了合成。[Photosensitizer] ・D-1: IRGACURE OXE 01 (manufactured by BASF Corporation) ・D-2: ADEKA NCI-930 (manufactured by ADEKA CORPORATION) ・D-3: a compound of the following structure (2:1 description indicates each structure Contains molar ratio.) [Chemical formula 45]

The above D-3 was synthesized according to the synthesis method described in International Publication No. 2017/217292.

〔Heat crosslinking agent〕 ・E-1: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD)

〔Silane Coupling Agent〕 ・F-1: N-(3-(Triethoxysilyl)propyl) o-formamide benzoic acid ・F-2: IM-1000 (manufactured by JX Nippon Mining & Metals Corporation) ・F-3: Benzophenone-3,3’-bis(N-(3-triethoxysilyl)propylamide)-4,4’-dicarboxylic acid

[Thermal base generator] ・G-1: A compound of the following structure [Chemical formula 46]

〔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 sulfide In Table 1, Table 2, or Table 3, the description in the “ratio in solvent” column indicates the content (mass %) of each solvent with respect to the total mass of the solvent.

<Evaluation> [Measurement of surface free energy] In each of the Examples and Comparative Examples except Examples 23 and 24, the thermosetting photosensitive composition or the comparative composition was applied to each of the Examples and Comparative Examples by the slit coating method. On a flat 4-inch silicon wafer, dried on a hot plate at 80°C for 5 minutes to form a film with a thickness of the “film thickness (μm)” listed in Table 1, Table 2 or Table 3 The thermosetting photosensitive layer A having a thickness of 150% and the thermosetting photosensitive layer B having a film thickness of 50% of the thickness described in the "film thickness (μm)" column of Table 1, Table 2 or Table 3. 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 1-22 were formed. In each Example and Comparative Example, the cured film A was produced by heating the thermosetting photosensitive layer A at 250° C. for 120 minutes. After that, the water contact angle and the diiodomethane contact angle of the cured film A were measured, and based on these contact angles, the surface free energy A (mJ/m ² ) was calculated using equation (1). ^{In each of the Examples and Comparative Examples, the surface free energy B (mJ/m 2} ) was calculated for the thermosetting photosensitive layer B by the same method as the surface free energy A described above. ^{The absolute value (mJ/m 2} ) of the difference between the above-mentioned surface free energy A and the above-mentioned surface free energy B is described in the column of “absolute value of the difference in surface free energy” in Table 1, Table 2 or Table 3. ^{The value of the surface free energy A (mJ/m 2} ) is described in the column of “surface free energy of cured film A” in Table 1, Table 2, or Table 3. The absolute value of the difference between the surface free energy A and the surface free energy B and the difference between the absolute value of the surface free energy A and the surface free energy B and the surface free energy A in the column of "absolute value/surface free energy of cured film A" in Table 1, Table 2 or Table 3 The ratio of the value (percentage, %).

[Evaluation of substrate step suitability] A film of OFPR (trade name, manufactured by TOKYO OHKA KOGYO CO., LTD.) as a photoresist is formed on an 8-inch round silicon wafer, and formed into the following shape by photolithography (A groove-like step of 30 μm in length, 30 μm in width, and 4 μm in depth is arranged every 50 μm in both the vertical and horizontal directions.) Repeat the pattern, use the pattern as a mask, and use an etching device (RIE-Samco Inc. RIE- 10N) Perform dry etching and peel off the pattern made of OFPR with acetone, thereby forming a step with a depth of 4μm as a step substrate. In each of 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 the slit coating method, respectively. In Examples 23 and 24, the resin layer 1 was formed by applying the thermosetting photosensitive composition to the stepped substrate by the spin coating method, respectively. The stepped substrate to which the obtained resin layer 1 was applied was dried on a hot plate at 80°C for 5 minutes, thereby obtaining the "film thickness (μm)" with an average thickness of Table 1, Table 2 or Table 3 on the stepped substrate "The thickness of the thermosetting photosensitive layer 1 described in the column." After that, using a stepper (Nikon NSR 2005 i9C), the entire surface of the obtained thermosetting photosensitive layer 1 was exposed to i-rays with an exposure energy of ^{500 mJ/cm 2.} 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. Heat the exposed thermosetting photosensitive layer 1 in a nitrogen atmosphere at a heating rate of 10°C/min. After reaching the temperature listed in the "hardening temperature" column of Table 1, Table 2 or Table 3, it will The cured film 1 was obtained by heating while maintaining the "curing time" in Table 1, Table 2 or Table 3 at the temperature described in the "Curing temperature" column. Using the slit coating method, the thermosetting photosensitive composition used to form the resin layer 1 or the same composition as the comparative composition was again applied to the surface of the obtained cured film 1 to form the resin layer 2. The stepped substrate to which the obtained resin layer 2 was applied was dried on a hot plate at 80°C for 5 minutes, thereby obtaining the "film thickness (μm)" column of Table 1, Table 2 or Table 3 on the stepped substrate The average thickness of the thermosetting photosensitive layer 2 described in. The thermosetting photosensitive layer 2 was subjected to the same i-ray exposure and heating as the thermosetting photosensitive layer 1 to obtain a cured film 2. The surface of the obtained cured film 2 on the side opposite to the cured film 1 was checked for the presence or absence of streaks (striated unevenness) and the surface roughness Ra was measured, and evaluated in accordance with the following evaluation criteria. Using the atomic force microscope Dimension FastScan AFM (manufactured by Bruker Corporation), the surface roughness of the cured film 2 was measured by measuring the surface roughness of the cured film 2 including the part with a step in the vertical direction and the part without a step in the range of 50 μm×50 μm. Degree Ra. The evaluation results are described in the "substrate step suitability" column of Table 1, Table 2 or Table 3. It can be said that no streaks are found and the smaller the surface roughness Ra is, the more the occurrence of coating defects is suppressed.

-Evaluation criteria- A: The occurrence of streaks is not observed and the surface roughness Ra is less than 3 μm. B: The occurrence of streaks is not observed and the above-mentioned surface roughness Ra is 3 μm or more. C: The occurrence of streaks is found.

[Evaluation of pattern formation] In each of the Examples and Comparative Examples except Examples 23 and 24, the thermosetting photosensitive composition or the comparative composition was applied to the above-mentioned stepped substrate by the slit coating method. The resin layer 1 is formed up. In Examples 23 and 24, the resin layer 1 was formed by applying the thermosetting photosensitive composition to the stepped substrate by the spin coating method, respectively. The stepped substrate on which the resin layer was formed was dried on a hot plate at 80°C for 5 minutes, thereby forming the "film thickness (μm)" column of Table 1, Table 2 or Table 3 on the stepped substrate Thermally hardened photosensitive layer 1 of average thickness. After that, using a stepper (Nikon NSR 2005 i9C), the entire surface of the obtained thermosetting photosensitive layer 1 was exposed to i-rays with an exposure energy of ^{500 mJ/cm 2.} 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. Heat the exposed thermosetting photosensitive layer 1 in a nitrogen atmosphere at a heating rate of 10°C/min. After reaching the temperature listed in the "hardening temperature" column of Table 1, Table 2 or Table 3, it will The cured film 1 was obtained by heating while maintaining the "curing time" in Table 1, Table 2 or Table 3 at the temperature described in the "Curing temperature" column. Using the slit coating method, the thermosetting photosensitive composition used to form the resin layer 1 or the same composition as the comparative composition was again applied to the surface of the obtained cured film 1 to form the resin layer 2. The stepped substrate to which the obtained resin layer 2 was applied was dried on a hot plate at 80°C for 5 minutes, thereby obtaining the "film thickness (μm)" column of Table 1, Table 2 or Table 3 on the stepped substrate The average thickness of the thermosetting photosensitive layer 2 described in. A stepper (Nikon NSR 2005 i9C) was used to expose the thermosetting photosensitive layer 2 to obtain the exposed thermosetting photosensitive layer. Exposure was performed with i-rays, and the exposure amount at a wavelength of 365 nm was set to 400 mJ/cm ² . In addition, exposure was performed using a photomask formed with a 1:1 line and space pattern with a line width of 10 μm. Exposure was carried out in such a way that a line and a space pattern crossed the step. 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. Regarding the example described as "K-1" in the column of "Developer" in Table 1, Table 2 or Table 3, the thermosetting photosensitive layer 2 after exposure was developed using cyclopentanone for 60 seconds and washed with PGMEA For 20 seconds, the layer pattern was obtained. Regarding the example described as "K-2" in the column of "Developer" in Table 1, Table 2 or Table 3, the development was carried out for 5 minutes with a 2.38% by mass tetramethylammonium hydroxide aqueous solution and rinsed with pure water for 20 seconds. , Thereby obtaining the pattern of the layer. The pattern (line pattern) of the layer after the development was observed with a scanning electron microscope (SEM) and evaluated in accordance with the following evaluation criteria. It can be said that pattern collapse or residue does not occur, and the closer the pattern is to a rectangle, the better the pattern formability.

-Evaluation criteria- A: Pattern collapse and residue did not occur, and a rectangular pattern was obtained. B: Pattern collapse and residue did not occur, but the pattern is not rectangular. C: Pattern collapse or residue occurred.

From the above results, it can be seen that the thermosetting photosensitive composition of the present invention can be suppressed even when a cured film is formed on an uneven substrate and other layers are further formed on the obtained cured film. Defects are generated on the layer, and the thermosetting photosensitive composition includes at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor , Sensitizers, surfactants and solvents, based on 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, and the free surface of the cured film A calculated by the formula (1) The absolute value of the difference between the energy and the surface free energy of the cured film B is 30% or less of the surface free energy of the cured film A. The thermosetting photosensitive composition of Comparative Example 1 and Comparative Example 2 does not contain a surfactant. Regarding the thermosetting photosensitive composition of 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. It can be seen that when the thermosetting photosensitive composition of Comparative Example 1 to Comparative Example 3 is applied to a non-uniform substrate to produce a cured film, and another layer is further formed on the obtained cured film, the above-mentioned other effects cannot be suppressed. Defects on the layer.

<Example 101> The thermosetting photosensitive composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface by the spin coating method, and dried at 80°C for 5 minutes After forming a thermosetting photosensitive composition layer with a thickness of 30 μm, exposure was performed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Through a mask (a binary mask with a pattern of 1:1 lines and spaces and a line width of 10 μm), exposure was performed at a wavelength of 365 nm. After exposure, it was developed with cyclopentanone for 60 seconds and washed with PGMEA for 20 seconds to obtain a layer pattern. Next, the temperature was raised at a temperature increase rate of 10° C./min under a nitrogen atmosphere, and after reaching 180° C., the temperature was maintained at 180° C. for 120 minutes, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, as a result of fabricating semiconductor devices using these interlayer insulating films for rewiring layers, normal operation was confirmed.

no.

Claims (15)

A thermosetting photosensitive composition for forming a thermosetting photosensitive layer. The aforementioned thermosetting photosensitive composition comprises: selected from the group consisting of polyimide, polyimide precursor, and polybenzoxazole And at least one resin in the group of polybenzoxazole precursors; sensitizer; surfactant; and solvent, according to the contact with water on the surface of the following cured film A and the surface of the following cured film B, respectively The absolute value of the difference between the surface free energy of the following cured film A and the surface free energy of the following cured film B calculated using the following formula (1) is the contact angle between the angle and the diiodomethane. The surface of the following cured film A 30% or less of free energy; Cured film A: After the coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 150% of the average thickness of the thermosetting photosensitive layer, The cured film of the thermosetting photosensitive composition obtained when heated at 250°C for 120 minutes; Cured film B: the coating film of the thermosetting photosensitive composition is 50% of the average thickness of the thermosetting photosensitive layer % Of the film thickness is formed on a flat support and heated at 250°C for 120 minutes to obtain a cured film of the aforementioned thermosetting photosensitive composition;

In the above formula (1), γ _s ^d represents the dispersed component of the surface free energy of the cured film, γ _s ^h represents the polar component of the surface free energy of the cured film, and γ _L ^d represents the surface free energy of water or diiodomethane. Dispersion component, γ _L ^h represents the polar component of the surface free energy of _{water or diiodomethane, γ L} ^tоtal represents the surface free energy of water or diiodomethane, and cоsθ represents the contact angle of water or diiodomethane; where, surface free energy Expressed as the sum of the dispersed component and the polar component, the dispersed component of the surface free energy of water is set to 21.7mJ/m ² , the polar component of the surface free energy of water is set to 50.8mJ/m ² , and the surface of diiodomethane The dispersion component of free energy was 48.1 mJ/m ² , and the polar component of the surface free energy of diiodomethane was 1.3 mJ/m ² . The thermosetting photosensitive composition according to claim 1, wherein The content of the aforementioned surfactant exceeds 0.1% by mass with respect to the total mass of the thermosetting photosensitive composition. The thermosetting photosensitive composition according to claim 1, wherein The content of the aforementioned surfactant is less than 0.005% by mass relative to the total mass of the thermosetting photosensitive composition. The thermosetting photosensitive composition according to any one of claims 1 to 3, wherein The aforementioned surfactants include surfactants that do not have fluorine atoms and silicon atoms. The thermosetting photosensitive composition according to any one of claims 1 to 3, wherein The content of the hydrocarbon-based surfactant in the thermosetting photosensitive composition is 50% by mass or more with respect to the total content of the surfactant. The thermosetting photosensitive composition according to any one of claims 1 to 3, wherein The aforementioned resin includes at least one resin selected from the group consisting of polyimine and polyimide precursors. The thermosetting photosensitive composition according to any one of claims 1 to 3, which is used to form a thermosetting photosensitive layer based on a slit coating method. The thermosetting photosensitive composition according to any one of claims 1 to 3, which is used to form a thermosetting photosensitive layer based on a spin coating method. The thermosetting photosensitive composition according to any one of claims 1 to 3, which is used to form an interlayer insulating film for a rewiring layer. A cured film formed by curing the thermosetting photosensitive composition according to any one of claims 1 to 9. A laminate comprising two or more layers of the cured film according to claim 10, and including a metal layer between any of the cured films. A method for manufacturing a hardened film, which includes a film forming process of applying the thermosetting photosensitive composition according to any one of claims 1 to 9 to a substrate to form a film. The method for producing a cured film according to claim 12, which includes an exposure process for exposing the film and a development process for developing the film. The method for producing a cured film according to claim 12 or claim 13, which includes a heating process of heating the aforementioned film at 50°C to 450°C. A semiconductor device comprising the cured film according to claim 10 or the laminated body according to claim 11.