TWI857161B - Pattern forming method, photosensitive resin composition, method for manufacturing laminate, and method for manufacturing semiconductor element - Google Patents

Abstract

The present invention provides a pattern forming method in which the obtained pattern has an excellent shape, a photosensitive resin composition used in the above pattern forming method, a method for manufacturing a laminate including the above pattern forming method, and a method for manufacturing an electronic component including the above pattern forming method. The pattern forming method includes: a first area exposure process, selectively exposing a part of the photosensitive film composed of the photosensitive resin composition, namely the first area; a second area exposure process, selectively exposing the second area; and a developing process, developing the photosensitive film after the second area exposure process, at least a part of the area included in the above first area and at least a part of the area included in the above second area are common areas, and the above photosensitive resin composition includes a specific resin and a photosensitive agent.

Description

Pattern forming method, photosensitive resin composition, method for manufacturing laminate, and method for manufacturing semiconductor element

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

Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulation properties, and therefore can be used for various purposes. The above-mentioned uses are not particularly limited, but if a semiconductor element for actual mounting is taken as an example, a pattern containing such resins can be used as a material or protective film for an insulating film or a sealing material. In addition, a pattern containing such resins is also used as a base film or a cover film of a flexible substrate.

For example, in the above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of a photosensitive resin composition containing the resin or its precursor. For example, the photosensitive resin composition is applied to a substrate by coating, and then exposed, developed, heated, etc. as needed, so that a cured resin can be formed on the substrate. The photosensitive resin composition can be applied by a known coating method, so it can be said that the manufacturing adaptability is excellent, such as the high degree of freedom in designing the shape, size, and application position of the applied photosensitive resin composition. In addition to the high performance of polyimide, polybenzoxazole, etc., the excellent adaptability in manufacturing is considered, and the application of photosensitive resin compositions containing these resins in the industry is increasingly expected to expand.

For example, Patent Document 1 describes a method for curing a photosensitive resin composition, which is characterized in that a photosensitive resin composition composed of a polybenzoxazole precursor and diazoquinone is exposed, developed, and patterned, and then the entire composition is exposed and cured.

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-146273

In the past, a photosensitive resin composition containing polyimide or polybenzoxazole and a precursor thereof was applied to a substrate and exposed and developed, and then heated as needed to form a pattern. In the formation of the above-mentioned pattern, it is desired to provide a pattern forming method in which the shape of the obtained pattern is excellent.

The object of the present invention is to provide a pattern forming method in which the obtained pattern has an excellent shape, a photosensitive resin composition used in the above-mentioned pattern forming method, a method for manufacturing a laminate including the above-mentioned pattern forming method, and a method for manufacturing an electronic component including the above-mentioned pattern forming method.

Hereinafter, examples of representative embodiments of the present invention are shown. ＜1＞ A pattern forming method, comprising: A first area exposure process, which is to selectively expose a first area, which is a part of a photosensitive film composed of a photosensitive resin composition; A second area exposure process, which is to selectively expose a second area, which is a part of the photosensitive film after the first area exposure process; and A developing process, which is to develop the photosensitive film after the second area exposure process, At least a part of the area included in the first area and at least a part of the area included in the second area are common areas, The photosensitive resin composition includes at least one resin selected from the group including polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, and a photosensitive agent. <2> The pattern forming method as described in <1>, which includes: a third area exposure process, which is to selectively expose a part of the photosensitive film after the second area exposure process, namely the third area; and a fourth area exposure process, which is to selectively expose a part of the photosensitive film after the third area exposure process, namely the fourth area, the above-mentioned development process is a process for developing the photosensitive film after the fourth area exposure process, at least a part of the area included in the third area and at least a part of the area included in any one of the first area, the second area and the fourth area are a common area, and at least a part of the area included in the fourth area and at least a part of the area included in any one of the first area, the second area and the third area are a common area. <3> A pattern forming method as described in <1> or <2>, wherein in a process of exposing a part of the photosensitive film before the above-mentioned development process, the time from the end of a certain exposure process to the start of another exposure process and excluding the time of other exposure processes is 0.1 seconds or more. <4> A pattern forming method as described in any one of <1> to <3>, wherein the exposure wavelength in the above-mentioned first area exposure process and the above-mentioned second area exposure process is 300 to 450nm. <5> A pattern forming method as described in any one of <1> to <4>, wherein the film thickness of the photosensitive film composed of the above-mentioned photosensitive resin composition is 10μm or more. <6> A pattern forming method as described in any one of <1> to <5>, wherein an organic solvent is used as a developer to carry out development in the above-mentioned development process. <7> A method for forming a pattern as described in any one of <1> to <6>, wherein the area of the area included in both the first region and the second region is 50% to 100% relative to the total area of the first region. <8> A method for forming a pattern as described in any one of <1> to <7>, wherein the resin is a polyimide precursor. <9> A method for forming a pattern as described in any one of <1> to <8>, wherein the resin has a free radical polymerizable group. <10> A method for forming a pattern as described in any one of <1> to <9>, wherein the photosensitive resin composition further comprises a free radical crosslinking agent. <11> A method for forming a pattern as described in any one of <1> to <10>, wherein the photosensitive resin composition further comprises a sensitizer. <12> A photosensitive resin composition, which is used to form the above-mentioned photosensitive film in the pattern forming method described in any one of <1> to <11>. <13> A method for manufacturing a laminate, which includes the pattern forming method described in any one of <1> to <11>. <14> A method for manufacturing an electronic component, which includes the pattern forming method described in any one of <1> to <11> or the method for manufacturing a laminate described in <13>. [Effect of the invention]

According to the present invention, a method for forming a pattern having an excellent shape, a photosensitive resin composition used in the above-mentioned pattern forming method, a method for manufacturing a laminate including the above-mentioned pattern forming method, and a method for manufacturing an electronic component including the above-mentioned pattern forming method are provided.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments indicated. In this specification, the numerical range indicated by the symbol "～" indicates a range including the numerical values before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only indicates an independent process, but also includes processes that cannot be clearly distinguished from other processes as long as the desired effect of the process can be achieved. Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes exposure using particle beams such as electron beams and ion beams, in addition to exposure using light, unless otherwise specified. In addition, as light used for exposure, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other actinic rays or radiation can be cited. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "acryl" and "methacryl". 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 means the total mass of the components excluding the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and 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 obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV (ultraviolet) detector with a wavelength of 254nm. In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that other layers exist on the upper or lower side of the reference layer among the multiple layers concerned. That is, a third layer or a third element may be further sandwiched between the reference layer and the other layers mentioned above, and the reference layer and the other layers mentioned above do not need to be in contact. In addition, unless otherwise specified, the direction of stacking layers on the substrate is called "upper", or when there is a photocurable layer, the direction from the substrate toward the photocurable layer is called "upper", and the opposite direction is called "lower". In addition, the setting of these upper and lower directions is for the convenience of this specification, and in actual forms, the "upper" direction in this specification may also be different from the vertical upper direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds that meet the requirements of the component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all compounds that meet the requirements of the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of the best state is the best state.

(Pattern forming method) The pattern forming method of the present invention includes: a first area exposure process, selectively exposing a part of a photosensitive film composed of a photosensitive resin composition, namely a first area; a second area exposure process, selectively exposing a part of a photosensitive film after the first area exposure process, namely a second area; and a developing process, developing the photosensitive film after the second area exposure process, at least a part of the area included in the first area and at least a part of the area included in the second area are common areas, and the photosensitive resin composition includes at least one resin selected from the group including polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor (hereinafter, also referred to as "specific resin"), and a photosensitive agent.

The pattern obtained in the pattern forming method of the present invention has an excellent shape. The mechanism for obtaining the above effect is not yet clear, but it can be inferred as follows.

In the past, a photosensitive film formed of a photosensitive resin composition containing polyimide or polybenzoxazole or a precursor thereof and a photosensitive agent was exposed and developed, and then heated as needed to form a pattern. As a result of in-depth research, the inventors found that by performing the above-mentioned first area exposure process and the above-mentioned second area exposure process on the photosensitive film formed by the above-mentioned photosensitive resin composition, the shape of the pattern after exposure and development can be suppressed from becoming a cone or an inverted cone. This is presumably because by performing the exposure in the first area exposure process and the second area exposure process instead of a single exposure, the amount of free radicals, acids, etc. generated from the photosensitive agent due to a single exposure can be reduced, and as a result, the diffusion of the above-mentioned free radicals, acids, etc. in the photosensitive film is suppressed. In the present invention, the angle between the surface of the substrate on which the pattern is formed and the side surface of the pattern is called a taper angle, and the shape of the pattern when the taper angle is significantly less than 90° (for example, when the taper angle is less than 80°, etc.) is called an inverted taper, and the shape of the pattern when the taper angle is significantly greater than 90° (for example, when the taper angle is greater than 100°, etc.) is called a taper. In the present invention, the excellent shape of the pattern means that the taper angle is close to 90°. For example, when the photosensitive film is a negative photosensitive film described later, it is considered that the photosensitive film, especially in the portion of the photosensitive film on the side of the exposure light source in the thickness direction of the photosensitive film, has a strong energy of the exposure light, so that the photosensitive agent is easily exposed to light, such as easily generating free radicals, acids, etc. Furthermore, it is believed that in the part of the photosensitive film on the side opposite to the exposure light source in the thickness direction of the photosensitive film (for example, the substrate side), the exposure light is weakened and the energy of the exposure light is weak, so the photosensitive agent is not easily exposed to light, for example, it is not easy to generate free radicals, acids, etc. As a result, the degree of hardening of the composition differs between the above-mentioned exposure light source side and the above-mentioned substrate side in the photosensitive film, so it is believed that the pattern shape is easy to become an inverted cone. Furthermore, when the photosensitive film is a positive photosensitive film described later, it is believed that the photosensitive agent is easily exposed to light, for example, it is easy to generate acid, especially on the exposure light source side in the thickness direction of the photosensitive film, because the energy of the exposure light is strong. Furthermore, it is believed that on the side opposite to the exposure light source in the thickness direction of the photosensitive film (for example, the substrate side), the exposure light is weakened and the energy is weak, so the photosensitive agent is not easily exposed to light, for example, it is not easy to generate acid. As a result, the solubility of the composition in the developer differs between the exposure light source side and the substrate side in the photosensitive film, so it is believed that the pattern shape is likely to become a cone. When the exposure is divided into a first area exposure process and a second area exposure process to expose such a negative photosensitive film or a positive photosensitive film, there is a time when no exposure is performed between the first area exposure process and the second area exposure process, so it is believed that the subsequent diffusion of free radicals, acids, etc. is suppressed, and the pattern shape is suppressed from becoming an inverted cone or a cone.

Patent document 1 neither describes nor suggests a pattern forming method including a first area exposure process and a second area exposure process. The pattern forming method of the present invention is described in detail below.

The pattern forming method of the present invention includes a first area exposure process and a second area exposure process. In addition, the pattern forming method of the present invention may further include a third area exposure process, a fourth area exposure process, other exposure processes, etc. described later in addition to the first area exposure process and the second area exposure process. In the present invention, the first area exposure process, the second area exposure process, the third area exposure process, the fourth area exposure process, other exposure processes, etc., which include the exposure of the photosensitive film, are also simply collectively referred to as "exposure processes".

<First area exposure process> The pattern forming method of the present invention includes a first area exposure process for exposing a portion of a photosensitive film composed of a photosensitive resin composition. In the first area exposure process, the photosensitive agent described later is exposed to light, and the solubility of the photosensitive film in the developer changes. Specifically, for example, when the photosensitive agent is a photopolymerization initiator described later, polymerization is carried out in the photosensitive film, and the solubility of the photosensitive film in the developer after the first area process decreases. Also, for example, when the photosensitive agent is a photoacid generator described later, and the developer is an alkaline developer described later, acid is generated in the photosensitive film, and the solubility in the developer increases. Furthermore, for example, when the photosensitive agent is a photoacid generator described later and the developer is an organic solvent described later, acid is generated in the photosensitive film and the solubility in the developer decreases. As described above, in the first area exposure process, the photosensitive agent can be used to promote the bonding reaction between the crosslinking group contained in the specific resin or crosslinking agent and other groups, thereby changing the solubility of the photosensitive film in the developer. The solubility of the photosensitive film in the developer can also be changed by using the product generated by the chemical change based on the photosensitive agent.

That is, the photosensitive film in the present invention can be a positive photosensitive film or a negative photosensitive film. The positive photosensitive film refers to a photosensitive film in which the exposed portion (exposed portion) is removed by a developer in the exposure process such as the first area exposure process and the second area exposure process, and the negative photosensitive film refers to a photosensitive film in which the portion (non-exposed portion) not exposed in the above exposure process is removed by a developer. In addition, in the present invention, the photosensitive film that utilizes the catalytic effect of the acid generated from the photosensitive agent by exposure is also called a chemically amplified photosensitive film. The chemically amplified photosensitive film preferably includes a resin having a polar conversion group such as an acid-decomposable group and a photoacid generator. The thickness of the photosensitive film is not particularly limited, but from the perspective of easily obtaining the effects of the present invention, 5 μm or more is preferred, and 10 μm or more is more preferred. The upper limit of the thickness is not particularly limited, but 50 μm or less is preferred, and 30 μm or less is more preferred.

Regarding the exposure wavelength in the first area exposure process, it can be appropriately set as the wavelength to which the photosensitive agent described later has sensitivity. 190-580nm is preferred, 240-550nm is more preferred, 300-450nm is further preferred, and 300-420nm is particularly preferred.

Regarding exposure wavelength, if we describe it in terms of its relationship with the light source (exposure method), we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (g, h, i-rays) ray (3 wavelengths), (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, (7) second harmonic wave (wavelength 532nm) and third harmonic wave (wavelength 355nm) of YAG laser, etc. Regarding the photosensitive resin composition of the present invention, exposure based on i-ray is preferred. In this way, high exposure sensitivity can be obtained in particular. From the perspective of operability and productivity, a wide (3 wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred. Furthermore, exposure using a laser light source such as a semiconductor laser is preferred from the perspectives that there is no need to use a mask pattern such as a photomask, even if a mask pattern is used, the degree of freedom of use is increased, it is easy to remove unnecessary wavelengths or to increase exposure illumination and shorten the exposure time, or it is possible to extend the life of the exposure light source.

As a method of exposing a portion of the photosensitive film in the first area exposure process, there can be cited an exposure method using a known mask, an exposure method of exposing a portion of the photosensitive film by laser exposure, etc.

<Second area exposure process> The pattern forming method of the present invention includes a second area exposure process which is performed after the first area exposure process and selectively exposes a part of the photosensitive film after the first area exposure process, namely, the second area. The second area exposure process can be performed in the same manner as the first area exposure process, except that at least a part of the area included in the first area and at least a part of the area included in the second area are common areas.

Regarding the exposure wavelength in the second area exposure process, it can be appropriately set as the wavelength to which the photosensitizer described later has sensitivity, 190 to 580 nm is preferred, 240 to 550 nm is more preferred, 300 to 450 nm is further preferred, and 300 to 420 nm is particularly preferred. In addition, the exposure wavelength in the second area exposure process can be the same as the exposure wavelength in the first area exposure process, or it can be different, but it is preferred that they are the same.

The exposure method in the second area exposure process is not particularly limited, and the same exposure method as the exposure method in the first area exposure process can be used. In addition, the exposure method in the second area exposure process can be the same as the exposure method in the first area exposure process, or can be different, but the same is preferred.

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

<Third area exposure process, fourth area exposure process> The pattern forming method of the present invention includes a third area exposure process for selectively exposing a portion of the photosensitive film after the second area exposure process, namely, the third area. The developing process is a process for developing the photosensitive film after the third area exposure process. It is preferred that at least a portion of the third area and at least a portion of the first area or the second area are a common area. Furthermore, the pattern forming method of the present invention includes a third area exposure process for selectively exposing a portion of the photosensitive film after the second area exposure process, namely, the third area, and a fourth area exposure process for selectively exposing a portion of the photosensitive film after the third area exposure process, namely, the fourth area. The developing process is a process for developing the photosensitive film after the fourth area exposure process. At least a portion of the area included in the third area and at least a portion of the area included in any one of the first area, the second area, and the fourth area are a common area, and it is preferred that at least a portion of the area included in the fourth area and at least a portion of the area included in any one of the first area, the second area, and the third area are a common area.

The third area exposure process and the fourth area exposure process can be performed by the same method as the first area exposure process. In addition, the exposure wavelengths in the third area exposure process and the fourth area exposure process can be the same as the exposure wavelength in the first area exposure process, or they can be different, but it is better to be the same. In addition, the exposure methods in the third area exposure process and the fourth area exposure process can be the same as the exposure method in the first area exposure process, or they can be different, but it is better to be the same.

The ratio of the area of the area included in the third area and at least any one of the first area, the second area and the fourth area to the total area of the third area is preferably 50-100%, 70-100% is more preferably, 80-100% is further preferably, and 90-100% is particularly preferably. Setting the above ratio to 100% is also one of the preferred embodiments of the pattern forming method of the present invention. The ratio of the area of the area included in the fourth area and at least any one of the first area, the second area and the third area to the total area of the fourth area is preferably 50-100%, 70-100% is more preferably, 80-100% is further preferably, and 90-100% is particularly preferably. Setting the above ratio to 100% is also one of the preferred embodiments of the pattern forming method of the present invention.

<Other exposure processes> The pattern forming method of the present invention may further include other exposure processes other than the first area exposure process, the second area exposure process, the third area exposure process, and the fourth area exposure process after the fourth area exposure process. The pattern forming method of the present invention includes other exposure processes for selectively exposing a part of the photosensitive film after the fourth area exposure process, i.e., other areas. The developing process is a process for developing the photosensitive film after the other exposure process. It is preferred that at least a part of the area included in the other area and at least a part of the area included in any of the first area, the second area, the third area, the fourth area, and other areas in another other exposure process are common areas. Other exposure processes can be performed by the same method as the first area exposure process. Furthermore, other exposure processes may be processes for exposing the entire photosensitive film (whole exposure) rather than processes for exposing a portion of the photosensitive film composed of a photosensitive resin composition. Furthermore, the exposure wavelength in other exposure processes may be the same as the exposure wavelength in the first area exposure process, or may be different, but it is preferred that they are the same. Furthermore, the exposure methods in other exposure processes may be the same as the exposure methods in the first area exposure process, or may be different, but it is preferred that they are the same. Regarding the process for exposing the photosensitive film (including the above-mentioned first area exposure process, the above-mentioned second area exposure process, the above-mentioned third area exposure process, the above-mentioned fourth area exposure process, and the above-mentioned other exposure processes), the pattern forming method of the present invention preferably includes 2 to 10 times in total, preferably includes 3 to 8 times, and more preferably includes 4 to 7 times.

The ratio of the area of the area included in the other areas and at least in any one of the first area, the second area, the third area, the fourth area and other areas in another exposure process to the total area of the other areas is preferably 50-100%, more preferably 70-100%, further preferably 80-100%, and particularly preferably 90-100%. Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention. Furthermore, the ratio of the total area of the regions exposed more than twice to the total area of the regions exposed at least once in the photosensitive film is preferably 50 to 100%, more preferably 70 to 100%, further preferably 80 to 100%, and particularly preferably 90 to 100%. Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention.

<Interval> In the pattern forming method of the present invention, in the process of exposing a part of the photosensitive film before the above-mentioned development process, the time from the end of a certain exposure process to the start of another exposure process excluding the time of other exposure processes is preferably 0.1 seconds or more, 0.5 seconds or more is more preferably, 1 second or more is further preferably, and 5 seconds or more is particularly preferably. The upper limit of the above-mentioned time is not particularly limited, for example, it can be set to 24 hours or less. In the present invention, the time from the end of a certain exposure process to the start of another exposure process excluding the time of other exposure processes is also referred to as "interval". It is believed that by setting the above-mentioned interval, the diffusion of free radicals, acids, etc. generated by the photosensitization of the photosensitive agent is suppressed and the pattern shape is excellent. For example, when the photosensitive film is a photosensitive film that contains a crosslinking agent and the like, and the solubility in the developer changes due to the crosslinking of the components in the photosensitive film (polymerization of free radical crosslinking agent or crosslinking of other crosslinking agents, etc.), it is believed that crosslinking occurs during the above interval, and the mobility of the field decreases. Therefore, it is believed that the diffusion of free radicals, acids, etc. generated when further exposed after the interval is suppressed. Also, for example, when the photosensitive film is a photosensitive film that contains a specific resin having a polar conversion group such as an acid-decomposable group and the like, and the solubility in the developer changes due to the structural changes such as deprotection of the components in the photosensitive film, it is believed that the polarity of the field increases during the above interval, and the diffusibility of the polar molecules decreases. Therefore, it is believed that the diffusion of acids, etc. generated when further exposed after the interval is suppressed. For example, when a total of 4 exposures from the first area exposure process to the fourth area exposure process are performed as the exposure process, the exposure can be performed in the order of the first area exposure process, 10 seconds interval, the second area exposure process, 10 seconds interval, the third area exposure process, 10 seconds interval, and the fourth area exposure process. When the process includes more than 3 times of exposure of the photosensitive film, there are multiple intervals between the above exposures, and the multiple intervals can be the same or different. Moreover, when there are multiple intervals, it is preferred that at least one interval among the multiple intervals is 0.1 seconds or more, 0.5 seconds or more is more preferred, 1 second or more is further preferred, and 5 seconds or more is particularly preferred. The upper limit of the above interval is not particularly limited, for example, it can be set to less than 24 hours. For example, as another example, when a total of 4 exposures from the first area exposure process to the fourth area exposure process are performed as the exposure process, the exposure can also be performed in the order of the first area exposure process, 5 seconds interval, the second area exposure process, 10 seconds interval, the third area exposure process, 15 seconds interval, and the fourth area exposure process. In addition, conversely, when a total of 4 exposures from the first area exposure process to the fourth area exposure process are performed as the exposure process, the exposure can also be performed in the order of the first area exposure process, 15 seconds interval, the second area exposure process, 10 seconds interval, the third area exposure process, 5 seconds interval, and the fourth area exposure process.

<Exposure wavelength> In the above-mentioned aspect, the exposure wavelength in the first area exposure process and the second area exposure process in the pattern forming method of the present invention is preferably 300-450nm, and 300-420nm is more preferably. In addition, when the pattern forming method of the present invention includes the third area exposure process and the fourth area exposure process, the exposure wavelength in the first area exposure process, the second area exposure process, the third area exposure process, and the fourth area exposure process is preferably 300-450nm, and 300-420nm is more preferably.

<Exposure amount> In the pattern forming method of the present invention, the exposure amount of the photosensitive film exposed by the first area exposure process, the second area exposure process, and the like (the total exposure amount in the photosensitive film based on multiple exposures such as the first area exposure process, the second area exposure process, and the third area exposure process) is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , calculated by the exposure energy at the wavelength to which the photosensitive agent has sensitivity. In addition, the focal position in the multiple exposures can be the same or different. The exposure amount in each process such as the first area exposure process and the second area exposure process is not particularly limited. As long as the total is within the above-mentioned exposure amount range, the exposure amount in each process can be the same or different. Furthermore, the exposure output in each process such as the first area exposure process and the second area exposure process can be the same or different. For example, in the second area exposure process, it is also preferable to perform exposure at a higher exposure output than in the first area exposure process. When performing a total of four exposures from the first area exposure process to the fourth area exposure process, it is also preferable to perform exposure at a high exposure output equivalent to that of the subsequent process.

<Post-exposure heating process> The pattern forming method of the present invention may include a post-exposure heating process (post-exposure heating process). The post-exposure heating process may be performed after the exposure process such as the first area exposure process and the second area exposure process and before the development process, or may be performed once after the first area exposure process and once after the second area exposure process each time the photosensitive film is exposed, or may determine whether to perform the post-exposure heating process each time the photosensitive film is exposed. The heating temperature in the post-exposure heating process is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating process is preferably 1 minute to 300 minutes, and more preferably 5 minutes to 120 minutes. Regarding the heating rate in the post-exposure heating process, it is preferably 1 to 12°C/minute from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/minute, and even more preferably 3 to 10°C/minute. In addition, the heating rate can be appropriately changed during the heating period. There is no particular limitation on the heating method in the post-exposure heating process, and a known heating plate, oven, infrared heater, etc. can be used. In addition, when heating, it is also preferably carried out in an atmosphere with a low oxygen concentration by circulating an inert gas such as nitrogen, helium, and argon.

<Film-forming process> The pattern-forming method of the present invention may include a film-forming process for forming a photosensitive film from a photosensitive resin composition. The photosensitive film in the first area exposure process may be a photosensitive film formed by a film-forming process, or may be a photosensitive film obtained by a purchase method or the like. The film-forming process is preferably a process for applying a photosensitive resin composition to a substrate to form a film (layer) and obtain a photosensitive film.

[Substrate] The type of substrate can be appropriately set according to the purpose, but there is no particular limitation. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates of plasma display panels (PDP). In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and casting substrates are more preferred. In addition, a bonding layer, an oxide layer, and the like may be provided on the surface of the substrates. In addition, the shape of the substrate is not particularly limited, and it can be circular or rectangular. A layer such as a close contact layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like can be provided on the surface of the substrate. In addition, the shape of the substrate is not particularly limited, and it can be circular or rectangular. As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm. In addition, as the substrate, for example, a plate-shaped substrate (substrate) is used.

Furthermore, when a photosensitive film is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a base material.

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

Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of uniform thickness of the photosensitive film, spin coating, slit coating, spray coating, and inkjet coating are more preferred. From the perspective of easily obtaining the effects of the present invention, slit coating is preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a photosensitive film of a desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Depending on the viscosity of the photosensitive resin composition or the set film thickness, it is also preferred to apply at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Furthermore, in order to obtain a uniform film thickness, multiple rotation speeds can be combined for coating. Furthermore, a method of transferring a coating formed by pre-imparting the coating on a pseudo support by the above-mentioned imparting method to a substrate can also be applied. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used. Furthermore, a process of removing excess film at the end of the substrate can also be performed. Examples of such processes include edge bead removal (EBR), air knife, back rinsing, etc. The following pre-wetting process may also be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

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

<Developing process> The pattern forming method of the present invention includes a developing process for obtaining a pattern by developing the above-mentioned photosensitive film after exposure with a developer. By developing, one of the exposed part and the non-exposed part is removed. There is no particular limitation on the developing method as long as the desired pattern can be formed. For example, it can be sprayed with a nozzle, sprayed with a mist, immersed in the developer of the substrate, etc., and it is preferably sprayed with a nozzle. The developing process can adopt a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer using ultrasound, etc., and a process of combining these.

Development is performed using a developer. As a developer, if it is negative development, a developer that removes the unexposed part (non-exposed part) can be used, and if it is positive development, a developer that removes the exposed part (exposed part) can be used, and there is no particular limitation. Regarding the development in the development process of the present invention, it is preferred to use an organic solvent as a developer, and it is more preferred to use a developer containing 50% or more of the organic solvent relative to the total mass of the developer as a developer. In addition, the developer may contain a known surfactant. In the present invention, the case where an alkaline developer is used as a developer is referred to as alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent relative to the total mass of the developer is used as a developer is referred to as solvent development.

In alkali development, a developer having an organic solvent content of 10 mass % or less relative to the total mass of the developer is preferred, a developer having an organic solvent content of 5 mass % or less is more preferred, a developer having an organic solvent content of 1 mass % or less is further preferred, and a developer containing no organic solvent is particularly preferred. The developer in alkali development is preferably an aqueous solution having a pH of 10 to 15. As the alkali compound contained in the developer in alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia or amine can be cited. As amines, for example, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, etc. can be cited. Among them, alkali compounds that do not contain metal are preferred, and ammonium compounds are more preferred. As alkali compounds, for example, when TMAH is used, the content of TMAH relative to the total mass of the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and further preferably 0.3 to 3 mass%. The alkali compound may be only one or more than two. When there are two or more alkali compounds, it is preferred that the total is within the above range.

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

As for the organic solvent, examples of the esters include preferably ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.) ), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl propionate)), methyl 2-alkoxy-2-methylpropionate 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 acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl Examples of the preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and examples of the preferred aromatic hydrocarbons include toluene, xylene, anisole, limonene, and examples of the preferred sulfoxides include dimethyl sulfoxide.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. In addition, when the developer contains an organic solvent, one organic solvent can be used or two or more organic solvents can be used in combination. The developer may further contain other components. As other components, for example, known surfactants and known defoaming agents can be cited. [Developer supply method] As long as the desired pattern can be formed, the developer supply method is not particularly limited, and examples include a method of immersing the substrate in the developer, a method of supplying the developer on the substrate with a nozzle, or a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include direct current nozzles, shower head nozzles, and mist nozzles. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, it is preferable to supply developer with a direct current nozzle or to supply developer continuously with a mist nozzle. From the perspective of developer permeability to the image area, it is more preferable to supply developer with a mist nozzle. In addition, the following process can be adopted: after continuously supplying the developer with a DC nozzle, the substrate is rotated to remove the developer from the substrate, and after rotating and drying, the developer is continuously supplied with a DC nozzle again, and the substrate is rotated to remove the developer from the substrate, and the process can be repeated several times. In addition, as a method for supplying the developer in the developing process, a process of continuously supplying the developer on the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer on the substrate using ultrasound, etc., and a process combining these processes can be adopted.

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

In the development process, after the treatment with the developer, further rinsing can be performed. Alternatively, a method such as supplying a rinsing solution before the developer in contact with the pattern is completely dried can be adopted. In the case of solvent development, it is preferred to use an organic solvent different from the developer for rinsing. In the case of alkali development, it is preferred to use pure water for rinsing. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing solution during rinsing is not particularly limited, but is preferably 10 to 45°C, and more preferably 18°C to 30°C. When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (e.g., 3- Alkoxy propionic acid methyl esters, 3-alkoxy propionic acid ethyl esters, etc. (for example, 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example, 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl esters, etc. (for example, 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid ethyl ester)), 2-alkoxy-2-methyl propionic acid methyl ester and 2-alkoxy-2-methyl propionic acid ethyl ester (for example, 2-methoxy-2-methyl As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate can be preferably cited. etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned. When the rinse liquid contains an organic solvent, one organic solvent can be used or two or more organic solvents can be used in combination. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred. When the rinse liquid contains an organic solvent, it is preferred that 50% by mass or more of the rinse liquid is an organic solvent, it is more preferred that 70% by mass or more of the rinse liquid is an organic solvent, and it is further preferred that 90% by mass or more of the rinse liquid is an organic solvent. Furthermore, 100% by mass of the rinse liquid can be an organic solvent. The rinse liquid may further contain other components. As other components, for example, a known surfactant and a known defoaming agent can be cited. [Method of supplying the rinse liquid] As long as the desired pattern can be formed, the method of supplying the rinse liquid is not particularly limited, and examples include a method of immersing the substrate in the rinse liquid, liquid development on the substrate, a method of supplying the rinse liquid to the substrate with a shower head, and a method of continuously supplying the rinse liquid to the substrate by a direct current nozzle. From the perspective of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency of manufacturing, it is better to supply the rinse liquid using a shower nozzle, a direct current nozzle, a spray nozzle, etc., and it is better to supply it continuously using a spray nozzle. From the perspective of the permeability of the rinse liquid to the image area, it is better to supply it using a spray nozzle. There is no particular limitation on the type of nozzle, and direct current nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing process is preferably a process in which a rinsing liquid is supplied or continuously supplied to the film after exposure using a direct current nozzle, and a process in which a rinsing liquid is supplied using a spray nozzle is more preferred. In addition, as a method for supplying the rinsing liquid in the rinsing process, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept on the substrate in a substantially static state, a process in which the rinsing liquid is vibrated on the substrate using ultrasound or the like, and a process in which these are combined can be adopted.

<Heating process> The manufacturing method of the present invention preferably includes a process (heating process) of heating the developed film. In the heating process, for example, when the photosensitive film contains a precursor such as a polyimide precursor or a polybenzoxazole precursor, or when the photosensitive film contains a crosslinking component such as a crosslinking agent, a cured pattern (also called a "cured film") can be obtained. It is preferred to include a heating process after the film formation process (layer formation process), the drying process, and the development process. In the heating process, for example, crosslinking of unreacted crosslinking agents can be performed. As the heating temperature (maximum heating temperature) of the middle layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is further preferred, 150°C or higher is further preferred, 160°C or higher is further preferred, and 170°C or higher is further preferred. As the upper limit, 500°C or lower is preferred, 450°C or lower is more preferred, 350°C or lower is further preferred, 250°C or lower is further preferred, and 220°C or lower is further preferred.

Regarding heating, it is preferred that the heating rate be 1 to 12°C/minute from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/minute, and even more preferably 3 to 10°C/minute. By setting the heating rate to 1°C/minute or more, it is possible to ensure productivity while preventing excessive volatilization of acid or solvent, and by setting the heating rate to 12°C/minute or less, it is possible to alleviate the residual stress of the pattern. In addition, in the case of an oven capable of rapid heating, it is preferred that the heating rate be 1 to 8°C/second from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/second, and even more preferably 3 to 6°C/second.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when a photosensitive resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), and it is preferably to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition.

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

In particular, when forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is not yet certain, but it is believed that this is because the acetylene groups of the specific resin between the layers undergo a cross-linking reaction.

Heating can be performed in stages. For example, the pre-treatment process can be performed by heating from 25°C to 180°C at 3°C/min and maintaining at 180°C for 60 minutes, and then heating from 180°C to 200°C at 2°C/min and maintaining at 200°C for 120 minutes. The heating temperature of the pre-treatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pre-treatment process, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. The properties of the membrane can be improved by such pre-treatment processes. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a process of more than two stages, for example, pretreatment process 1 can be performed in the range of 100 to 150°C, and then pretreatment process 2 can be performed in the range of 150 to 200°C.

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

Regarding the heating process, it is better to carry out the process in an atmosphere with low oxygen concentration by circulating inert gases such as nitrogen, helium, and argon in order to prevent the decomposition of specific resins. The oxygen concentration is preferably 50ppm (volume ratio) or less, and more preferably 20ppm (volume ratio) or less. There is no particular limitation on the heating method in the heating process, and examples thereof include a heating plate, an infrared furnace, an electric oven, and a hot air oven.

<Metal layer forming process> The pattern forming method of the present invention preferably includes a metal layer forming process in which a metal layer is formed on the surface of the pattern after the first area exposure process, the second area exposure process, and the like.

The metal layer is not particularly limited, and existing metals can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

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

<Application> As fields to which the pattern obtained by the pattern forming method of the present invention can be applied, there can be cited insulating films for semiconductor elements, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, there can be cited sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or situations in which patterns are formed by etching insulating films for actual mounting purposes such as the above. For such applications, for example, reference can be made to Science & Technology Co., Ltd., “Advanced Functionality and Application Technology of Polyimide”, April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, “Fundamentals and Development of Polyimide Materials”, November 2011, and Japan Polyimide and Aromatic Polymer Research Society, “Latest Polyimide: Fundamentals and Applications”, NTS, August 2010.

Furthermore, the pattern obtained by the pattern forming method of the present invention can also be used in the manufacture of offset printing plates or screen plates, the use of etched parts, the manufacture of protective varnishes and dielectric layers in electronics, especially microelectronics, etc.

(Manufacturing method of laminate) The manufacturing method of the laminate of the present invention preferably includes the pattern forming method of the present invention. The laminate obtained by the manufacturing method of the laminate of the present invention is a laminate including two or more layers of patterns, and may also be a laminate including 3 to 7 layers. The pattern included in the laminate of the present invention may be the above-mentioned cured film. Among the above-mentioned two or more layers of patterns included in the above-mentioned laminate, at least one is a pattern obtained by the pattern forming method of the present invention. From the viewpoint of improving the shape of the pattern, it is preferred that all the patterns included in the above-mentioned laminate are patterns obtained by the pattern forming method of the present invention. Regarding the above-mentioned laminate, it is preferred that it includes more than two patterns and includes a metal layer between any of the above-mentioned patterns. It is preferred that the above-mentioned metal layer is formed by the above-mentioned metal layer forming process. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers stacked in sequence, namely, a first pattern, a metal layer, and a second pattern, can be cited as a preferred one. It is preferred that both the above-mentioned first pattern and the above-mentioned second pattern are patterns obtained by the pattern forming method of the present invention. The photosensitive resin composition of the present invention used to form the above-mentioned first pattern and the photosensitive resin composition of the present invention used to form the above-mentioned second pattern can be a composition of the same composition or a composition of different compositions. The metal layer in the multilayer body of the present invention can be preferably used as a metal wiring such as a redistribution layer.

<Lamination process> The method for manufacturing a laminated body of the present invention preferably includes a lamination process. The lamination process includes a series of processes including (a) a film forming process (layer forming process), (b) a first area exposure process, (c) a second area exposure process, and (d) a developing process, which are performed again in sequence on the surface of the pattern or metal layer. However, it is possible to perform processes after the (b) first area exposure process after repeating the film forming process of (a). Furthermore, after the above-mentioned (c) second area exposure process, a process for exposure such as one or more third area exposure processes, fourth area exposure processes, etc. may be included. Furthermore, after the above-mentioned (d) developing process, the above-mentioned heating process may be included. Furthermore, after the (d) development process, the above-mentioned metal layer forming process may be included. It is needless to say that the above-mentioned drying process may be further included in the lamination process as appropriate.

When further performing a layering process after the layering process, a surface activation process may be further performed after the exposure process, after the development process, after the heating process, or after the metal layer forming process. As the surface activation process, plasma treatment may be exemplified.

The above-mentioned lamination process is preferably performed 2 to 5 times, and more preferably 3 to 5 times. For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer can be cited, wherein the number of resin layers is 2 or more and 20 or less, 3 or more and 7 or less, and 3 or more and 5 or less. In addition, each layer in the lamination process may be the same in composition, shape, film thickness, etc., or may be different. <Surface activation treatment process> The method for producing a cured film of the present invention may include a surface activation treatment process of performing a surface activation treatment on at least a portion of the above-mentioned metal layer and the photosensitive resin composition layer. The surface activation treatment process is usually performed after the metal layer forming process, but the metal layer forming process may be performed after the above-mentioned exposure and development process and after the photosensitive resin composition layer is subjected to the surface activation treatment process. The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed only on at least a portion of the exposed photosensitive resin composition layer, or may be performed on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred that the surface activation treatment be performed on at least a portion of the metal layer, and it is preferred that the surface activation treatment be performed on a portion or the entire region of the metal layer where the photosensitive resin composition layer is formed on the surface. As described above, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. In addition, it is preferred that the surface activation treatment be performed on a portion or the entirety of the photosensitive resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer or the resin layer disposed on the surface subjected to the surface activation treatment can be improved. Specifically, the surface activation treatment may be selected from plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment of removing oxide film by immersion in aqueous hydrochloric acid solution and then immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1,000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

In the present invention, it is particularly preferred that after the metal layer is provided, a pattern of the photosensitive resin composition is further formed by covering the metal layer. Specifically, a pattern of (a) film formation process (layer formation process), (b) first area exposure process, (c) second area exposure process, (d) development process, and (e) metal layer formation process is repeated in this order. By alternately performing the above-mentioned processes (a) to (d) for forming a pattern and the metal layer formation process, the pattern and the metal layer can be alternately stacked.

(Method for manufacturing electronic components) The present invention also discloses a method for manufacturing a semiconductor component including the pattern forming method of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor component in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, and such contents are incorporated into this specification. The following describes the details of the photosensitive resin composition used in the pattern forming method of the present invention, the method for manufacturing a laminate of the present invention, or the method for manufacturing a semiconductor component of the present invention.

(Photosensitive resin composition) The photosensitive resin composition of the present invention is a photosensitive resin composition used in the pattern forming method of the present invention, the manufacturing method of the laminate of the present invention, or the manufacturing method of the semiconductor element of the present invention. The photosensitive resin composition of the present invention contains at least one resin selected from the group including polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, and a photosensitive agent. The following describes the details of each component contained in the photosensitive resin composition of the present invention.

<Specific resin> The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor. As the specific resin, the photosensitive resin composition of the present invention preferably contains polyimide or polyimide precursor, and more preferably contains polyimide precursor. In addition, the specific resin preferably has a free radical polymerizable group. When the specific resin has a radical polymerizable group, the photosensitive resin composition preferably includes the photoradical polymerization initiator described below as a photosensitive agent, more preferably includes the photoradical polymerization initiator described below as a photosensitive agent and includes the radical crosslinking agent described below, and further preferably includes the photoradical polymerization initiator described below as a photosensitive agent, includes the radical crosslinking agent described below, and includes the sensitizer described below. For example, a negative photosensitive layer is formed by such a photosensitive resin composition. In addition, the specific resin may have a polar conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably includes the photoacid generator described below as a photosensitive agent. For example, a positive-type photosensitive layer or a negative-type photosensitive layer of a chemically amplified type is formed from the photosensitive resin composition.

[Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably comprises a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. ^R111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably linear or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 6 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms or groups composed of these groups, and more preferably groups containing aromatic groups with 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ - or NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the preparation of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used. Specifically, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of aromatic groups include the following aromatic groups.

[Chemical formula 2] In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, NHCO-, or a combination thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -; and even more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -. In the formula, * indicates a bonding site with other structures.

As the diamine, specifically, there can be mentioned 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-diaminocyclohexane 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'- Dimethylcyclohexylmethane and isophoronediamine; meta-phenylenediamine or para-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'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone, 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, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminoterphenyl, 4, 4'-Bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4' -Diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)hexafluoropropane 1,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy) At least one of the following diamines: 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotoluidine and 4,4’-diaminoquaternaryl.

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

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

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

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 3] In formula (51), R ⁵⁰ to R ⁵⁷ are 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. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 4-1] In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms or trifluoromethyl groups. Examples of diamine compounds that impart the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These compounds may be used alone or in combination of two or more. The following diamines may also be preferably used. [Chemical Formula 4-2]

R ¹¹⁵ in 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 5] In formula (5), R ¹¹² preferably represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and NHCO-, and a group selected from the combination thereof; more preferably, it represents a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and SO ₂ -; and even more preferably, it represents a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and SO ₂ -.

Formula (6) [Chemical formula 6]

Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical Formula 7] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone 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'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

Moreover, as a more preferred example, tetracarboxylic dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes a residual group of a diaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxadiazole group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. As the free radical polymerizable group possessed by a polyimide precursor, a group having an ethylenic unsaturated bond is preferred. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

[Chemical formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, or a polyalkylene group. Preferred examples of R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group. An ethylene group, a propylene group, a trimethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group are more preferred. From the viewpoint of easily satisfying formula (2) in an organic film, a polyalkylene group is further preferred. In the present invention, a polyalkoxyl group refers to an alkoxyl group directly bonded to two or more groups. The alkylene groups of the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups are bonded to a plurality of propoxy groups is preferred, polyethyleneoxy or polypropoxy is more preferred, and polyethyleneoxy is further preferred. In the group in which a plurality of ethyleneoxy groups are bonded to a plurality of propoxy groups, the ethyleneoxy and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspects of the number of repetitions of ethoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, there can be mentioned an aromatic group and an aralkyl group having an acid group bonded to one, two or three (preferably one) carbon atoms constituting the aromatic group. Specifically, there can be mentioned an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, there can be mentioned a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably an OH group. It is also preferred that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferred, and an alkyl group substituted with an aromatic group is more preferred. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic. As the linear or branched alkyl group, for example, there can be mentioned a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a dibutyl group, a tertiary butyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and a 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy group. 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, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, bornadiyl, bicyclohexyl, and pinenyl. Among them, cyclohexyl is the most preferred from the viewpoint of high sensitivity. Furthermore, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred. The aromatic group specifically includes a substituted or unsubstituted benzene ring, a naphthyl ring, a pentylene ring, an indene ring, an azulene ring, a heptylene ring, an indenene ring, a perylene ring, a fused pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a fused tetraphenyl ring, a chrysene ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyridine ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, Indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinolone ring, naphthyl ring, naphthyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, phenanthroline ring, phenanthrene ring, phenanthrene ring, phenanthrene ring, phenanthrene ring or phenanthrene ring. Benzene ring is the most preferred.

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

At least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. An acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, and the like are preferred. From the viewpoint of exposure sensitivity, an acetal group is more preferred. Specific examples of the acid-decomposable group include a tertiary butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tertiary butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

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

In order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting such a structure, the exposure tolerance can be further expanded. Formula (2-A) [Chemical Formula 9] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), respectively, and their preferred ranges are also the same. R ¹¹² has the same meaning as R ¹¹² in formula (5), and its preferred range is also the same.

The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating units represented by formula (2). In addition to the repeating units of formula (2), the polyimide precursor may contain other types of repeating units.

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

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 further preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further 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 further 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 further preferred, 3.2 or less is further preferred, 3.1 or less is further preferred, 3.0 or less is further preferred, and 2.95 or less is particularly preferred. In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight/number average molecular weight.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer having an organic solvent as a main component. In this specification, an alkali-soluble polyimide means that in 100 g of a 2.38 mass % tetramethylammonium aqueous solution, 0.1 g or more of the polyimide is dissolved at 23°C. From the viewpoint of pattern formation, it is preferred to dissolve 0.5 g or more of the polyimide, and it is further preferred to dissolve 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, and 100 g or less is preferred. In addition, from the perspective of the membrane strength and insulation of the obtained organic membrane, polyimide having multiple imide structures in the main chain is preferred. In this specification, "main chain" means the longest bond in the molecule of the polymer compound constituting the resin, and "side chain" means the other bonds.

-Fluorine atom- From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms. The fluorine atom is preferably contained in ^R132 in the repeating unit represented by formula (4) described later or ^R131 in the repeating unit represented by formula (4) described later, and is more preferably contained in ^R132 in the repeating unit represented by formula (4) described later or ^R131 in the repeating unit represented by formula (4) described later as a fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.

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

- Ethylenically unsaturated bonds - From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has ethylenically unsaturated bonds. The polyimide may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, preferably in the side chains. The above-mentioned ethylenically unsaturated bonds are preferably free radical polymerizable. ^R132 in the repeating unit represented by the formula (4) described later or R131 in the repeating unit represented by the formula (4) described later having an ethylenic unsaturated bond is preferred, and ^R132 in the repeating unit represented by the formula (4) described later or ^R131 in the repeating unit represented by the formula (4) described later as a group having an ethylenic unsaturated bond is more preferred. Among them, ^R131 in the repeating unit represented by the formula (4) described later having an ethylenic unsaturated bond is preferred, and ^R131 in the repeating unit represented by the formula (4) described later as a group having an ethylenic unsaturated bond ^is more preferred. Examples of the group having an ethylenic unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloxy group, and a group represented by the following formula (IV).

[Chemical formula 10]

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

In formula (IV), ^R21 represents an alkylene group having 2 to 12 carbon atoms, -O- _CH2CH (OH) _CH2- , -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of carbon atoms repeated is preferably 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group consisting of two or more of the above groups.

Among them, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 11] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom bonded to R ²⁰¹ in formula (III). In formulas (R1) to (R3), preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L are the same as preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in R ²¹ described above. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same. The structure represented by formula (R1) can be obtained by, for example, reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (e.g., 2-isocyanateethyl methacrylate, etc.). The structure represented by formula (R2) can be obtained by, for example, reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (e.g., 2-hydroxyethyl methacrylate, etc.). The structure represented by formula (R3) can be obtained by, for example, reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (e.g., glycidyl methacrylate, etc.).

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

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

-Crosslinking groups other than ethylenic unsaturated bonds- The polyimide may have crosslinking groups other than ethylenic unsaturated bonds. Examples of the crosslinking groups other than ethylenic unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutylene groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. The crosslinking groups other than ethylenic unsaturated bonds are preferably ^R131 contained in the repeating unit represented by formula (4) described later. The amount of crosslinking groups other than ethylenic unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

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

-Acid value- When polyimide is used for alkaline development, from the viewpoint of improving the developing property, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more. 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 using a developer having an organic solvent as the main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g. The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. In addition, as an acid group contained in the polyimide, from the viewpoint of both storage stability and developing properties, an acid group with a pKa of 0 to 10 is preferred, and an acid group with a pKa of 3 to 8 is more preferred. pKa is a dissociation reaction in which hydrogen ions are released from an acid and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In this manual, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, the values described in "Revised 5th Edition Chemical Handbook Basics" compiled by the Chemical Society of Japan can be referred to. Furthermore, when the acid group is a polyacid such as phosphoric acid, the above pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group including a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

- Phenolic hydroxyl group - From the viewpoint of making the development speed based on the alkaline 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 at the side chain. The phenolic hydroxyl group is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later. The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably comprises a repeating unit represented by the following formula (4), and more preferably comprises a repeating unit represented by the formula (4) and has a polymerizable group. Formula (4) [Chemical Formula 12] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When there is a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , or may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2). Formula (4-1) [Chemical Formula 13] In formula (4-1), R ¹³³ is a polymerizable group, and the meanings of other groups are the same as those in formula (4). Formula (4-2) [Chemical formula 14] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

The meaning of the polymerizable group is the same as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor, etc. R ¹³¹ represents a divalent organic group. As the divalent organic group, the same as R ¹¹¹ in formula (2) can be exemplified, and the preferred range is also the same. In addition, as R ¹³¹ , a diamine residue remaining after removing the amino group of a diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, the example of R ¹¹¹ in formula (2) of the polyimide precursor can be cited.

From the viewpoint of more effectively suppressing the generation of warp during firing, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule, and further preferably, it is a diamine containing no aromatic ring.

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

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same as R ¹¹⁵ in formula (2), and the preferred range is also the same. For example, the four connecting bonds 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 15]

^R132 may be a tetracarboxylic acid residue remaining after the anhydride group is removed from tetracarboxylic dianhydride. As a specific example, ^R115 in the formula (2) of the polyimide precursor may be cited. From the viewpoint of the strength of the organic film, ^R132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

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

Furthermore, the polyimide preferably has fluorine atoms in the structural unit. The content of fluorine atoms in the polyimide is preferably 10 mass % or more, and more preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

In order to improve the storage stability of the composition, the main chain ends of the polyimide are preferably sealed with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. Among them, monoamines are more preferably used. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidization rate (ring closure rate)- From the viewpoint of the film strength and insulation of the obtained organic film, the imidization rate (also called "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. The upper limit of the above-mentioned imidization rate is not particularly limited, and it can be 100% or less. For example, the above-mentioned imidization rate can be measured by the following method. Measure the infrared absorption spectrum of the polyimide, and determine the peak intensity P1 of the absorption peak originating from the imide structure, that is, near 1377cm ^-1 . Then, after the polyimide is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377cm ^-1 . The obtained peak intensities P1 and P2 can be used to calculate the imidization rate of the polyimide according to the following formula: Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

The polyimide may include repeating units of the above formula (4) each including one type of R ¹³¹ or R ¹³² , or may include repeating units of the above formula (4) including two or more different types of R ¹³¹ or R ^132. In addition to the repeating units of the above formula (4), the polyimide may also include other types of repeating units.

Polyimide can be prepared by, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound (part of which is substituted with a monoamine, i.e., a capping agent) at low temperature, a method of reacting tetracarboxylic dianhydride (part of which is substituted with an acid anhydride, a monoacyl chloride compound, or a monoactive ester compound, i.e., a capping agent) with a diamine compound at low temperature, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the resulting diester in the presence of a diamine (part of which is substituted with a monoamine, i.e., a capping agent) and a condensing agent, a method of reacting tetracarboxylic dianhydride with ... After obtaining a diester from a dianhydride and an alcohol, the remaining dicarboxylic acid is chlorinated and reacted with a diamine (part of which is substituted with a monoamine, i.e., a capping agent) to obtain a polyimide precursor, which is synthesized by a known imidization reaction method and a method of complete imidization, a method of stopping the imidization reaction midway and introducing a part of the imide structure, or a method of introducing a part of the imide structure by mixing a completely imidized polymer and its polyimide precursor. Commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation).

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

[Polybenzoxazole precursor] The polybenzoxazole precursor used in the present invention is not particularly limited in structure, but preferably comprises a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 16] In formula (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 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 the preferred ranges are also the same. That is, it is preferred that at least one is a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As a divalent organic group, it is preferred that it contains at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. It is preferred that R ¹²¹ is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

As the dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred. As the dicarboxylic acid containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred, and dicarboxylic acids composed of linear or branched (preferably linear) aliphatic groups and 2 -COOH groups are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. As the dicarboxylic acid containing a straight chain aliphatic group, there can be mentioned malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylheptanecarboxylic acid, Diacid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, hexadecanedioic acid, hexadecanedioic acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid Alkanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diethylene glycol acid, and dicarboxylic acid represented by the following formula, etc.

[Chemical formula 17] (In the formula, Z is a carbonyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

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

[Chemical formula 18] In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and * represents a bonding site with other structures independently.

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

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2), and the preferred range is also the same. Preferably, the group ¹²² is 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'-dihydroxydiphenylsulfonate, 4,4'-diamino-3,3'-dihydroxydiphenylsulfonate, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane. -(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. Such bisaminophenols can be used alone or in combination.

Among the diaminophenol derivatives, those having the following aromatic groups are preferred.

[Chemical formula 19] In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , -NHCO-, and * and # represent the bonding site with other structures. In addition, ^R122 is preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # in total are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded and two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded and two # are bonding sites to the oxygen atom to which R ^{122 in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R 122} in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

[Chemical formula 20]

In formula (As), _R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[Chemical formula 21] (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that the presence of a substituent at the adjacent position of the phenolic hydroxyl group, i.e., R3 _, is particularly preferred because the carbonyl carbon of the amide bond and the hydroxyl group are closer together and the effect of a high cyclization rate during curing at a low temperature is further improved.

In the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, high transparency to I-rays and a high cyclization rate effect during curing at a low temperature can be maintained, which is preferred.

Furthermore, in the above formula (As), it is further preferred that R ₁ is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group for _R1 include _-CH2- , _-CH ( _CH3 )-, -C( _CH3 ) _2- , -CH(CH2CH3) _{- ,} -C(CH3)( _CH2CH3 )-, -C _{( CH2CH3} )( _CH2CH3 )- _, -CH(CH2CH2CH3)-, -C(CH3 _{) ( CH2CH2CH3} )- _, -CH ₍ CH( _CH3 ) _{2 ) -} , _-C ( _{CH3 )} (CH( _CH3 ) _{2 ) - ,} -CH( _CH2CH2CH2CH3 )-, -C( _CH3 )(CH2CH2CH3)-, -C( _CH2CH ( _CH3 ) ₂ ) _- , _-C ( _{CH Among them} , _{-CH2- ,} -CH( _CH3 ) _- , and _-C ( _CH3 ) _{2- are more preferred from the} viewpoint of _{obtaining a polybenzoxazole} precursor having _an excellent balance _{between maintaining high} transparency _to I-rays _{and increasing the cyclization} rate during curing _{at low temperatures} while having sufficient solubility _{in a solvent} .

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506 can be referred to, and the contents thereof are incorporated into the present specification.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include the contents described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated into the present specification. Of course, the present invention is not limited to these.

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

[Chemical formula 22] In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining parts are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the molar % of the Z part, the molar % of the a structure is 5 to 95 molar %, the molar % of the b structure is 95 to 5 molar %, and the molar % of a+b is 100 molar %.

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

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

For example, when used in the composition described below, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further 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 further preferably 9,200 to 11,200. The molecular weight dispersion of the above polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a polymerizable group is more preferred. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. In addition, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid decomposable group. [Chemical Formula 23] In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When there is a polar conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the polar conversion group such as an acid-decomposable group may be located on at least one of R ¹³³ and R ¹³⁴ , or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [Chemical Formula 24] In formula (X-1), at least one of ^R135 and ^R136 is a polymerizable group or a polar conversion group such as an acid-decomposable group, and if not a polymerizable group or a polar conversion group such as an acid-decomposable group, it is an organic group, and the other groups have the same meanings as in formula (X). Formula (X-2) [Chemical Formula 25] In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the rest are substituents. The meanings of the other groups are the same as those in formula (X).

The meaning of the polymerizable group or the polarity converting group such as the acid-decomposable group is the same as the polymerizable group explained in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. As a specific example, R ¹²¹ in the formula (3) of the polybenzoxazole precursor can be cited. The preferred examples have the same meaning as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, R ¹²² in the formula (3) of the polybenzoxazole precursor can be cited as an example. Moreover, the meaning of the preferred example is the same as that of R ^122. For example, the four connecting bonds 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 26]

The polybenzoxazole has an oxadiazole rate of preferably 85% or more, and more preferably 90% or more. When the oxadiazole rate is 85% or more, the film shrinkage due to ring closure (occurring when oxadiazole is heated) is reduced, and the warping can be effectively suppressed.

The polybenzoxazole may include repeating units of the above formula (X) all containing one type of R ¹³¹ or R ¹³² , or may include repeating units of the above formula (X) containing two or more different types of R ¹³¹ or R ^132. In addition to the repeating units of the above formula (X), the polybenzoxazole may also include other types of repeating units.

For example, a diaminophenol derivative is reacted with a dicarboxylic acid containing R ¹³³ or a dicarboxylic acid dichloride and a dicarboxylic acid derivative selected from the above dicarboxylic acids to obtain a polybenzoxazole precursor, which is then oxazolidated by a known oxazolidation reaction method to obtain a polybenzoxazole. In addition, in the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative that has been reacted with 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield.

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 an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[Method for producing polyimide precursors, etc.] Polyimide precursors, etc. can be obtained by reacting dicarboxylic acid or dicarboxylic acid derivatives with diamines. It is preferably obtained by halogenating dicarboxylic acid or dicarboxylic acid derivatives with a halogenating agent and then reacting them with diamines. In the method for producing a polyimide precursor, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one or more. As the organic solvent, it can be appropriately set according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide can be produced by cyclizing a polyimide precursor after synthesizing it by thermal imidization, chemical imidization (for example, by promoting the cyclization reaction by the action of a catalyst), or by directly synthesizing the polyimide precursor.

-Capping agent- When manufacturing polyimide precursors, it is preferred to seal the ends of the polyimide precursors with a capping agent such as anhydride, monocarboxylic acid, monoacyl chloride, or monoactive ester compound in order to further improve storage stability. As the end-capping agent, it is more preferable to use a monoamine. As preferred compounds of the monoamine, there can be cited aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Solid precipitation- When manufacturing a polyimide precursor, etc., a solid precipitation process may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, thereby enabling solid precipitation. Thereafter, by drying the polyimide precursor, etc., a powdered polyimide precursor, etc. can be obtained.

[Content] The content of the resin in the composition of the present invention is preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, and 50% by mass or more, relative to the total solid content of the composition. In addition, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, 99% by mass or less is more preferred, 98% by mass or less is more preferred, 97% by mass or less is more preferred, and 95% by mass or less is more preferred relative to the total solid content of the composition. The composition of the present invention may contain only one resin or two or more. When containing two or more resins, the total amount is preferably within the above range.

<Other resins> The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins" for short). As other resins, polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable group value to the composition instead of or in addition to the polymerizable compound described below, the coating properties of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more relative to the total solid content of the composition. In addition, the content of the other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less relative to the total solid content of the composition. Furthermore, as one of the preferred embodiments of the composition of the present invention, it is also possible to set the composition to have a low content of other resins. In the above embodiment, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient. The composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, it is preferred that the total amount is within the above range.

<Photosensitive agent> The composition of the present invention contains a photosensitive agent. As the photosensitive agent, a photopolymerization initiator is preferred.

[Photopolymerization initiator] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it can be an activator that reacts with a photoexcited sensitizer to generate active radicals.

In the organic film, from the viewpoint of easily satisfying the above formula (2), it is preferable that the composition of the present invention contains the metal element-containing compound described later as a photo-radical polymerization initiator. That is, in the present invention, among the metal element-containing compounds described later, the metal element-containing compound having the ability to initiate free radical polymerization can be used as a photo-radical polymerization initiator. Among them, having the ability to initiate free radical polymerization means being able to generate free radicals that can initiate free radical polymerization. For example, when a composition containing a free radical polymerizable monomer, an adhesive polymer and a metal element-containing compound is irradiated with light in a wavelength region where the metal element-containing compound absorbs light but the free radical polymerizable monomer does not absorb light, the presence or absence of polymerization initiation ability can be confirmed by confirming whether the free radical polymerizable monomer disappears. When confirming whether it disappears, an appropriate method can be selected according to the type of the radical polymerizable monomer or the binder polymer, for example, confirmation by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography) can be used.

When the composition of the present invention contains a metal-containing compound having the ability to initiate free radical polymerization, it is also preferred that the composition of the present invention substantially does not contain a free radical polymerization initiator other than the above-mentioned metal-containing compound. Substantially not containing a free radical polymerization initiator other than the above-mentioned metal-containing compound means that the content of other free radical polymerization initiators other than the above-mentioned metal-containing compound in the composition of the present invention is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass. In addition, when the composition of the present invention contains a metal-containing compound having the ability to initiate free radical polymerization, it is also preferred that the composition of the present invention contains the above-mentioned metal-containing compound and other photo-free radical polymerization initiators. In the composition of the present invention, when a metal-containing compound and other photo-radical polymerization initiators are contained, the content of the metal-containing compound relative to the total content of the metal-containing compound and other photo-radical polymerization initiators is preferably 20 to 80 mass %, and more preferably 30 to 70 mass %. In addition, as the above-mentioned other photo-radical polymerization initiators, the oxime compound described later is preferred.

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

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

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

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

As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Publication No. 2009-191179, which has an absorption maximum wavelength matching a light source of wavelength such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF Corporation) can also be used.

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

As the photo-radical polymerization initiator, an oxime compound is more preferred. By using an oxime compound, the exposure tolerance can be further effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also function as a photohardening accelerator, so they are particularly preferred.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the composition of the present invention, it is particularly preferred to use the oxime compound as a photoradical polymerization initiator (oxime-based photopolymerization initiator). Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 27-1]

Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. 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 also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. In addition, oxime compounds having the following structures can also be used. [Chemical formula 27-2] As a photopolymerization initiator, an oxime compound having a fluorene ring can also be used. As a specific example of an oxime compound having a fluorene ring, a compound described in Japanese Patent Publication No. 2014-137466 and a compound described in Japanese Patent No. 06636081 can be cited. As a photopolymerization initiator, an oxime compound having a carbazole ring and at least one benzene ring being a naphthalene ring skeleton can also be used. As a specific example of such an oxime compound, a compound described in International Publication No. 2013/083505 can be cited.

Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

More preferred photoradical polymerization initiators are trihalogenomethyl trioxane compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to select at least one compound from the group consisting of trihalogenomethyl trioxane compounds, α-aminoketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds, and oxime compounds are further preferred.

In addition, as the photoradical polymerization initiator, benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-aminophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-amino-propanone-1, quinones obtained by condensation of an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. can be used. In addition, compounds represented by the following formula (I) can also be used.

[Chemical formula 28]

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

[Chemical formula 29]

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

Furthermore, the photoradical polymerization initiator may also include compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass % relative to the total solid content of the composition of the present invention. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[Photoacid generator] In addition, the composition of the present invention preferably contains a photoacid generator as a photosensitizer. By containing a photoacid generator, for example, acid is generated in the exposed part of the composition layer, and the solubility of the exposed part in the developer (for example, an alkaline aqueous solution) is increased, and a positive pattern in which the exposed part is removed by the developer can be obtained. In addition, by containing a photoacid generator and a polymerizable compound other than a free radical polymerizable compound described later, for example, the following state can be set: the crosslinking reaction of the polymerizable compound is promoted by the acid generated in the exposed part, and the exposed part is less likely to be removed by the developer than the non-exposed part. According to this state, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinone diazonium compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as acylimide sulfonates, oxime sulfonates, diazo disulfonates, disulfonates, and o-nitrobenzyl sulfonates.

As the quinone diazide compound, there can be mentioned those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester, those in which the sulfonic acid of quinone diazide is bonded to a polyamine compound via a sulfonamide bond, those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy polyamine compound via at least one of an ester bond and a sulfonamide bond, etc. In the present invention, for example, it is preferred that 50 mol% or more of the functional groups of the polyhydroxy compound and the polyamine compound are substituted with quinone diazide.

In the present invention, as quinone diazide, 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl can be preferably used. 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of mercury lamp, so it is suitable for i-ray exposure. 5-naphthoquinone diazide sulfonyl compound has absorption extending to the g-ray region of mercury lamp, so it is suitable for g-ray exposure. In the present invention, 4-naphthoquinone diazide sulfonyl compound and 5-naphthoquinone diazide sulfonyl compound are preferably selected according to the wavelength of exposure. Furthermore, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or it may contain a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using such naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, salts or ester compounds of such compounds, etc. can be cited.

As the onium salt compound or sulfonate salt compound, compounds described in paragraphs 0064 to 0122 of Japanese Patent Application Publication No. 2008-013646 can be cited. In addition, as the photoacid generator, commercially available products can be used. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation).

When a photoacid generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % relative to the total solid content of the composition of the present invention. The photoacid generator may be contained in one type or in two or more types. When two or more photoacid generators are contained, the total amount thereof is preferably within the above range.

<Solvent> The photosensitive resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfones, amides, ureas, and alcohols.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) Esters, etc.)), alkyl 2-alkoxypropionates (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate 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 acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. can be cited as preferred ones.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, dihydrolevoglucosanone and the like are preferably mentioned.

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

As the sulfoxides, for example, dimethyl sulfoxide can be preferably mentioned.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmethoxyphene, N-acetylmethoxyphene, etc. can be cited as preferred ones. As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. can be cited as preferred ones. As alcohols, there may be cited methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

Regarding solvents, from the perspective of improving the properties of the coated surface, it is better to mix two or more solvents.

In the present invention, one solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more of them is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone at the same time. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone is also preferred.

Regarding the content of the solvent, from the viewpoint of coating properties, it is preferably set to an amount where the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80 mass %, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 40 to 70 mass %. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

The solvent may be contained in one kind or in two or more kinds. When two or more kinds of solvents are contained, it is preferred that the total amount of the solvents is within the above range.

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed in the heating process described later, thereby further improving the solvent resistance.

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

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass % relative to the total solid content of the composition of the present invention, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass %. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the following effect: by generating an acid by heating, the cross-linking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzophenone compound is promoted.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if a substance that does not generate acid during drying (pre-baking: about 70 to 140°C) after the composition is applied to the substrate but generates acid during the final heating (hardening: about 100 to 400°C) after forming a pattern in the subsequent exposure and development is selected as the thermal acid generator, it is better to suppress the decrease in sensitivity during development. When the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule, the peak temperature of the lowest temperature heat peak is obtained as the thermal decomposition start temperature. As an instrument used to measure the thermal decomposition starting temperature, Q2000 (manufactured by TA Instruments) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or halogenated alkylsulfonic acids such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, a substance that generates an alkylsulfonic acid having 1 to 4 carbon atoms or a halogenated alkylsulfonic acid having 1 to 4 carbon atoms is more preferred as a thermal acid generator, such as (4-hydroxyphenyl)dimethylcopperium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium methanesulfonate, benzyl (4-hydroxyphenyl)methylcopperium methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylcopperium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium methanesulfonate, and trifluoromethanesulfonate (4- Preferred are (4-(((methoxycarbonyl)oxy)phenyl)dimethylcopperthionate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperthionate, (4-hydroxyphenyl)methylcopperthionate, (4-((methoxycarbonyl)oxy)phenyl)methylcopperthionate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperthionate trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, the compound described in 0059 of Japanese Patent Application Laid-Open No. 2013-167742 is also preferably used as the thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic film. In addition, from the perspective of the electrical insulation of the organic film, 20 parts by mass or less is preferably, 15 parts by mass or less is more preferably, and 10 parts by mass or less is even more preferably.

<Onium salt> The composition of the present invention preferably contains an onium salt. In particular, when a polyimide precursor is contained as another resin, the composition preferably contains an onium salt. The type of onium salt is not particularly limited, and ammonium salts, imide salts, cobalt salts, iodine salts, or phosphonium salts can be preferably cited. Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodine salts, or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

Furthermore, the onium salt is a salt of a cation and anion having an onium structure, and the cation and anion may be bonded by covalent bonding or not. That is, the onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt having cation molecules and anion molecules of different molecules bonded by ion, and the intermolecular salt is preferred. Furthermore, in the composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by ion bonding or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a coronium cation, an iodine cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, coronium cations and iodine cations is more preferred.

The onium salt used in the present invention may also be a thermal alkali generator. The thermal alkali generator refers to a compound that generates a base by heating, for example, an acidic compound that generates a base when heated to 40°C or above.

[Ammonium salt] In the present invention, ammonium salt refers to a salt of ammonium cations and anions.

-Ammonium cation- As the ammonium cation, a quaternary ammonium cation is preferred. Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 30] In formula (101), R ¹ to R ⁴ each independently represents a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a alkyl group, more preferably an alkyl group or an aryl group, and further preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. ^{R 1} to R ⁴ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. When at least two of R ¹ to R ⁴ are bonded to form a ring, the ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2). [Chemical Formula 31]

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

-Anions- As the anion in the ammonium salt, one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions is preferred, and carboxylate anions are more preferred from the perspective of both stability and thermal decomposition of the salt. That is, the ammonium salt is preferably a salt of ammonium cation and carboxylate anions. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and an anion of a divalent carboxylic acid is more preferred. According to this aspect, the stability, curability and developability of the composition can be further improved. In particular, by using anions of divalent carboxylic acids, the stability, curability, and developing properties of the composition can be further improved.

The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 32] In formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group indicates that the Hammett substituent constant σm is a positive value. σm is described in detail in Yufu Mitsuno's General Commentary, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature. Examples of substituents having a positive σm include a _CF3 group (σm = 0.43), a _CF3C (=O) group (σm = 0.63), a HC≡C group (σm = 0.21), a _CH2 =CH group (σm = 0.06), an Ac group (σm = 0.38), a MeOC (=O) group (σm = 0.37), a MeC (=O)CH=CH group (σm = 0.21), a PhC (=O) group (σm = 0.34), and a _H2NC (=O) _CH2 group (σm = 0.06). Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same).

EWG is preferably a group represented by the following formula (EWG-1) to (EWG-6). [Chemical Formula 33] In formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical Formula 34] In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, -NR ^X - and combinations thereof, and ^RX represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion and an oxalate anion.

From the viewpoint that the cyclization of the specific resin is easy to proceed at low temperature and the storage stability of the composition is easy to improve, the onium salt in the present invention contains ammonium cation as the cation and the onium salt contains an anion with a pKa (pKaH) of 2.5 or less of the conjugated acid as the anion. It is more preferable to contain an anion of 1.8 or less. The lower limit of the above pKa is not particularly limited. From the viewpoint that the generated base is not easy to neutralize and the cyclization efficiency of the specific resin is improved, -3 or more is preferred, and -2 or more is more preferred. As the above pKa, the values described in Determination of Organic Structures by Physical Methods (author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; editor: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these references, values calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software were used.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 35]

[Imine salt] In the present invention, the imine salt refers to a salt of an imine cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-Imine cation- As the imine cation, pyridinium cation is preferred. Also, as the imine cation, a cation represented by the following formula (102) is preferred. [Chemical Formula 36]

In formula (102), ^R5 and ^R6 each independently represent a hydrogen atom or a alkyl group, ^R7 represents a alkyl group, and at least two of ^R5 to ^R7 may be bonded to form a ring. In formula (102), the meanings of ^R5 and ^R6 are the same as those of ^R1 to ^R4 in the above formula (101), and preferred embodiments are also the same. In formula (102), it is preferred that ^R7 is bonded to at least one of ^R5 and ^R6 to form a ring. The above ring may contain a heteroatom. As the above heteroatom, a nitrogen atom can be cited. In addition, as the above ring, a pyridine ring is preferred.

The imide cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical Formula 37] In formula (Y1-3) to (Y1-5), ^R101 represents an n-valent organic group, ^R5 has the same meaning as ^R5 in formula (102), ^R7 has the same meaning as ^R7 in formula (102), n represents an integer greater than 1, and m represents an integer greater than 0. In formula (Y1-3), ^R101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which they are bonded, and more preferably a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, or a group obtained by removing n hydrogen atoms from benzene or naphthalene. In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and more preferably 1. In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and more preferably 1.

As specific examples of imine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 38]

[Zirconium salt] In the present invention, the zinc salt refers to a salt of zinc cation and anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

- Copper cation - As the copper cation, a tertiary copper cation is preferred, and a triaryl copper cation is more preferred. In addition, as the copper cation, a cation represented by the following formula (103) is preferred. [Chemical Formula 39]

In formula (103), R ⁸ to R ¹⁰ each independently represent a alkyl group. R ⁸ to R ¹⁰ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups. From the viewpoint of synthetic suitability, it is preferred that they are the same group.

[Iodine salt] In the present invention, an iodine salt refers to a salt of an iodine cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

-Ion cation- As the iodine cation, a diaryl iodine cation is preferred. Also, as the iodine cation, a cation represented by the following formula (104) is preferred. [Chemical Formula 40]

In formula (104), R ¹¹ and R ¹² each independently represent a alkyl group. R ¹¹ and R ¹² each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹¹ and R ¹² may be the same group or different groups. From the perspective of synthetic suitability, it is preferred that they are the same group.

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

-Phosphonium cation- As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations. Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical Formula 41]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a alkyl group. R ¹³ to R ¹⁶ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups. From the viewpoint of synthetic suitability, it is preferred that they are the same group.

When the composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass % relative to the total solid content of the composition of the present invention. The lower limit is 0.5 mass % or more, which is more preferred, 0.85 mass % or more, which is further preferred, and 1 mass % or more is further preferred. The upper limit is 30 mass % or less, which is more preferred, 20 mass % or less, which is further preferred, and 10 mass % or less is further preferred. It can be 5 mass % or less, and can also be 4 mass % or less. One or more onium salts can be used. When two or more are used, the total amount is preferably within the above range.

<Thermoalkali generator> The composition of the present invention may contain a thermoalkali generator. In particular, when the composition contains a polyimide precursor as another resin, it is preferable that the composition contains a thermoalkali generator. The thermoalkali generator may be a compound that satisfies the above-mentioned onium salt, or may be another thermoalkali generator other than the above-mentioned onium salt. As another thermoalkali generator, a non-ionic thermoalkali generator may be mentioned. As a non-ionic thermoalkali generator, a compound represented by formula (B1) or formula (B2) may be mentioned. [Chemical Formula 42]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are independently an organic group, a halogen atom or a hydrogen atom that does not have a tertiary amine structure. However, Rb ¹ and Rb ² will not be hydrogen atoms at the same time. Moreover, Rb ¹ , Rb ² and Rb ³ do not have a carboxyl group. In addition, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the carbon atom to which the bond is formed is a carbon atom that forms a carbonyl group, that is, when it forms an amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and (B2), at least one of ^Rb1 , ^Rb2 and ^Rb3 preferably has a cyclic structure, and at least two of them more preferably have a cyclic structure. The cyclic structure may be a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring of two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and a cyclohexane ring is more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or aralkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms). These groups may have substituents within the range in which the effects of the present invention are exerted. ^Rb1 and ^Rb2 may be bonded to each other to form a ring. As the formed ring, a 4-7-membered nitrogen-containing heterocyclic ring is preferred. In particular, ^Rb1 and ^Rb2 are preferably linear, branched or cyclic alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms) which may have a substituent, more preferably cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms) which may have a substituent, and further preferably cyclohexyl groups which may have a substituent.

As Rb ³ , there can be mentioned alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Aralkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or aralkyloxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aralkenyl, and aralkyloxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 43]

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 have the same meanings as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within a range in which the effects of the present invention are exerted. Among them, ^Rb13 is preferably an aralkyl group.

^Rb33 and ^Rb34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

Rb ³⁵ is alkyl (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), alkenyl (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and aryl is preferred.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [Chemical Formula 44]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups. Rb ¹⁷ is alkyl (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), alkenyl (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein aryl is preferred.

The molecular weight of the non-ionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As the lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

Among the above-mentioned onium salts, as specific examples of compounds serving as thermal alkali generators or other specific examples of thermal alkali generators, the following compounds can be cited. [Chemical Formula 45] [Chemical formula 46]

[Chemical formula 47]

The content of the alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Crosslinking agent> The photosensitive resin composition of the present invention preferably contains a crosslinking agent. As the crosslinking agent, free radical crosslinking agents or other crosslinking agents can be cited.

<Free radical crosslinking agent> The photosensitive resin composition of the present invention may further preferably have a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the group containing the above-mentioned ethylenic unsaturated bond, there can be cited groups having ethylenic unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. Among them, as the group containing the above-mentioned ethylenic unsaturated bond, (meth)acryloyl is preferred, and from the viewpoint of reactivity, (meth)acryloyloxy is more preferred.

The radical crosslinking agent may be a compound having one or more ethylenic unsaturated bonds, and preferably a compound having two or more ethylenic unsaturated bonds. The compound having two ethylenic unsaturated bonds is preferably a compound having two groups containing the above-mentioned ethylenic unsaturated bonds. In addition, from the perspective of the film strength of the obtained pattern (cured film), it is preferred that the photosensitive resin composition of the present invention contains a compound having three or more ethylenic unsaturated bonds as a radical crosslinking agent. As the compound having more than 3 ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is preferred, a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenic unsaturated bonds is further preferred. Furthermore, the compound having more than 3 ethylenic unsaturated bonds is preferably a compound having more than 3 groups containing the above ethylenic unsaturated bonds, a compound having 3 to 15 is more preferred, a compound having 3 to 10 is further preferred, and a compound having 3 to 6 is particularly preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured film), it is also preferred that the photosensitive resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

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

As specific examples of free radical crosslinking agents, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and thiohydrides with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids can also be preferably used. Moreover, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and the substitution reaction products of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, the above-mentioned unsaturated carboxylic acid can be replaced by a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

In addition, the free radical crosslinking agent is preferably a compound having a boiling point of 100°C or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyletrol tri(meth)acrylate, neopentyletrol tetra(meth)acrylate, dipentyletrol penta(meth)acrylate, dipentyletrol hexa(meth)acrylate, hexylene glycol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the mixture. Acid-esterified compounds, (meth)acrylic acid urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 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, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be mentioned.

Furthermore, as preferred radical crosslinking agents other than the above, compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, and cardo resins described in Japanese Patent Application Laid-Open Nos. 2010-160418, 2010-129825, and 4364216, can also be used.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

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

In addition, the following compounds described as formula (1) and formula (2) together with specific examples thereof in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical crosslinking agents. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting the resulting mixture to (meth)acrylic esterification.

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

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

As commercially available free radical crosslinking agents, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc., which are bifunctional methacrylates having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentoxy chains, TPA-330, which is a trifunctional acrylate having three isobutyloxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (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 free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent can be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical crosslinking agents having an acid group, the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and the free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give it an acid group is more preferred. Particularly preferred is a free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give it an acid group, wherein the aliphatic polyhydroxy compound is a compound such as neopentyl triol or dipentyl triol. As commercially available products, for example, M-510, M-520, etc. can be cited as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, and the particularly preferred acid value is 5 to 30 mgKOH/g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in manufacturing is excellent, and the developing property is excellent. In addition, the polymerizability is good. In addition, from the perspective of the developing speed during alkaline development, the preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and the particularly preferred acid value is 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of suppressing the warping accompanying the control of the elastic modulus of the pattern (cured film), the photosensitive resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent. As the monofunctional free radical crosslinking agent, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical crosslinking agent, in order to suppress volatility before exposure, a compound having a boiling point of 100°C or more at normal pressure is also preferred. In addition, from the perspective of pattern resolution and film stretchability, it is also preferred to use a bifunctional methacrylate or acrylate. As a specific compound, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A EO adduct dimethacrylate, methacrylate 2-hydroxy-3-acryloyloxypropyl, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds. Two or more of these may be used in combination as needed.

When a free radical crosslinking agent is contained, its content is preferably more than 0 mass % and less than 60 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

The free radical crosslinking agent may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount thereof is preferably within the above range.

<Other crosslinking agents> The photosensitive resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. Compounds having multiple groups in the molecule that are promoted by the photosensitivity of the above-mentioned photosensitive agent (forming covalent bonds with other compounds in the composition or their reaction products) are preferred, and compounds having multiple groups in the molecule that are promoted by the action of acids or bases (forming covalent bonds with other compounds in the composition or their reaction products) are more preferred. The acid or base is preferably an acid or base generated from a photoacid generator or a photoalkali generator as a photosensitive agent in the exposure process such as the first area exposure process and the second area exposure process. As other crosslinking agents, compounds having at least one group selected from the group including hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred. As other crosslinking agents, for example, compounds having a structure in which an amino-containing compound such as melamine, acetylene urea, urea, alkyl urea, benzoguanamine, etc. reacts with formaldehyde or reacts with formaldehyde with an alcohol and replaces the hydrogen atom of the above amino group with a hydroxymethyl or alkoxymethyl group can be cited. The production method of these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds produced by the above method. In addition, they may be oligomers formed by self-condensation of hydroxymethyl groups of these compounds. As the above-mentioned amino-containing compounds, the crosslinking agent using melamine is called a melamine-based crosslinking agent, the crosslinking agent using acetylene urea, urea or alkyl urea is called a urea-based crosslinking agent, the crosslinking agent using alkyl urea is called an alkyl urea-based crosslinking agent, and the crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, the photosensitive resin composition of the present invention preferably comprises at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably comprises at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.

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

Specific examples of the urea crosslinking agent include monohydroxymethylated acetylene urea, dihydroxymethylated acetylene urea, trihydroxymethylated acetylene urea, tetrahydroxymethylated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetraethoxymethylated acetylene urea. , monopropoxymethylated acetylene urea, dipropoxymethylated acetylene urea, tripropoxymethylated acetylene urea, tetrapropoxymethylated acetylene urea, monobutoxymethylated acetylene urea, dibutoxymethylated acetylene urea, tributoxymethylated acetylene urea or tetrabutoxymethylated acetylene urea and other acetylene urea-based crosslinking agents; Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea, monohydroxymethylated Ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea and other ethylene urea crosslinking agents, monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea and other propylene urea crosslinking agents, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group including a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group including a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include terephthalic acid, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzene hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl ketone, methoxymethylbenzene methoxybenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-phenylenediol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercial products can be used. Preferred commercial products include 46DMOC, 46DMOEP (all 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 (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX-279, NIKALACMW-100LM, NIKALACMX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

In addition, the photosensitive resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds and benzophenone compounds as other crosslinking agents.

[Epoxy compounds (compounds having epoxy groups)] As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reaction below 200°C, and since dehydration reaction due to crosslinking does not occur, it is not easy to cause film shrinkage. Therefore, by containing epoxy compounds, low-temperature curing and warping of photosensitive resin compositions can be effectively suppressed.

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

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited to these. Specifically, the following can be cited: EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-485 0-150, 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 are product names, DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (these are trade names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, ADEKA CORPORATION), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, Serviners B0134, B0177 (these are trade names, 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 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (compounds having an oxycyclobutyl group)] Examples of the oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used alone or in combination of two or more.

[Benzotriazole compounds (compounds having benzoxazolyl groups)] Benzotriazole compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting the occurrence of warping.

Preferred examples of the benzophenone compound include B-a type benzophenone, B-m type benzophenone, P-d type benzophenone, F-a type benzophenone (these are trade names, manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resins, and novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

The content of other crosslinking agents is preferably 0.1 to 30 mass % relative to the total solid content of the photosensitive resin composition of the present invention, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %. Other crosslinking agents may contain only one or more. When containing two or more other thermal crosslinking agents, their total content is preferably within the above range.

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

[Compounds having a sulfonamide structure] The sulfonamide structure is represented by the following formula (S-1). [Chemical formula 48] In formula (S-1), R represents a hydrogen atom or an organic group, and R may bond with other structures to form a ring structure, and * independently represents the bonding site with other structures. It is preferred that the above R is the same group as ^R2 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 one sulfonamide structure is preferred.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 49] 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. It is preferred that 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 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 group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of the cycloalkyl group include cycloalkyl groups having 5 to 10 carbon atoms, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include 6 to 20 carbon atoms, and 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a pyrimidine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring.

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

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethylsulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethylsulfonamide.

[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical formula 50] In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group, ^R4 and ^R5 may bond to form a ring, ^R4 may bond to other structures bonded by * to form a ring structure, ^R5 may bond to other structures bonded by * to form a ring structure, and * each independently represents a bonding site to other structures.

^R4 and ^R5 are preferably independently a hydrogen atom. Examples of ^R4 and ^R5 include a hydrogen atom or 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 group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are cited. 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 the above-mentioned cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl can be mentioned. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. As the above-mentioned alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group can be mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferred, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferred. As the above-mentioned alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group can be 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. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a pyrimidine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring. 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.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 51] 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), ^R4 and ^R5 have the same meanings as ^R4 and ^R5 in formula (T-1), and preferred embodiments are also the same. In formula (T-2), ^R6 and ^R7 are preferably independently monovalent organic groups. In formula (T-2), preferred embodiments of monovalent organic groups in ^R6 and ^R7 are the same as preferred embodiments of monovalent organic groups in ^R4 and ^R5 in formula (T-1).

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

[Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the photosensitive resin composition of the present invention is preferably 0.05 to 10 mass %, more preferably 0.1 to 5 mass %, and further preferably 0.2 to 3 mass %. The photosensitive resin composition of the present invention may contain only one compound selected from the group including compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

<Migration inhibitor> The photosensitive resin composition of the present invention may preferably further contain a migration inhibitor. By containing the migration inhibitor, it is possible to effectively inhibit the migration of metal ions from the metal layer (metal wiring) into the photocurable layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, pyrimidine ring, 2H-pyran ring, 6H-pyran ring, triazole ring), compounds having thiourea and thiohydrin, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, and 4-methylbenzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that captures anions such as halogen ions may be used.

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

As specific examples of the migration inhibitor, the following compounds can be cited.

[Chemical formula 52]

When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass % relative to the total solid content of the photosensitive resin composition.

The number of migration inhibitors may be one or more. When the number of migration inhibitors is two or more, the total amount thereof is preferably within the above range.

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

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), phenathiophene, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso- Nitro-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine first barium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- Trioxane-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl radical, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

[Chemical formula 53]

When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20.0 mass %, more preferably 0.01 to 5 mass %, further preferably 0.02 to 3 mass %, and particularly preferably 0.05 to 2.5 mass % relative to the total solid content of the photosensitive resin composition of the present invention.

The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

<Metal Adhesion Improver> The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds with sulfonamide structures, compounds with thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[Chemical formula 54-1]

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used. As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3 -Acryloxypropyltrimethoxysilane, 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-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more. As aluminum-based bonding agents, for example, tri(ethyl acetylacetate)aluminum, tri(acetylacetone)aluminum, diisopropylaluminum ethyl acetylacetate, etc. can be cited.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and further preferably in the range of 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is better that the total is within the above range.

<Sensitizer> The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat, etc. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases. As the sensitizer, for example, michler's ketone, 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-dimethylaminophenylallylidenedihydroindanone, p-dimethyl aminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl Oxycarbonyl-7-dimethylaminocoumarin, 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-toluenediethanolamine, N-phenylethanolamine, 4-methylbenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene (1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetylamide, benzanilide, N-methylacetylanilide, 3',4'-dimethylacetylanilide, etc. In addition, a sensitizing dye can also be used as a sensitizer. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

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

<Other additives> The photosensitive resin composition of the present invention can be formulated with various additives as needed within the scope of obtaining the effects of the present invention, such as surfactants, chain transfer agents, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are formulated, it is preferred that the total amount thereof is set to 3% by weight or less of the solid content of the photosensitive resin composition. [Surfactant] From the perspective of further improving the coating properties, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating units of the side chains represent the number of repetitions of each repeating unit. [Chemical Formula 54-2] Furthermore, the surfactant may also include compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219. Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503 can be used. As a fluorine-based surfactant, a block polymer can also be used. As a specific example, the compound described in Japanese Patent Publication No. 2011-089090 can be cited. As a fluorine-based surfactant, a fluorine-containing polymer compound containing the following repeating units can also be preferably used: a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups (preferably ethoxy groups and propoxy groups). As for the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Application No. 2010-164965 can be cited, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation. The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of thickness of the coating film and liquid saving, and also has good solubility in the composition. Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH). Examples of hydrocarbon surfactants include Pionin A-76, Newkalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, and Pionin P-4050-T (all manufactured by TAKEMOTO OIL & FAT CO., LTD.). As the nonionic surfactant, there can be mentioned glycerol, trihydroxymethylpropane, trihydroxymethylethane and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (Boyd & Moore Executive Search.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (TAKEMOTO OIL & FAT CO., LTD.), Olfin E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd. . (made) etc. As cationic surfactants, specifically, organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc. can be cited. As anionic surfactants, specifically, W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by Sanyo Kasei Co., Ltd.), etc. can be cited. When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the photosensitive resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, the total amount thereof is preferably within the above range.

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

In addition, the chain transfer agent may also include compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be only one or two or more. When there are two or more chain transfer agents, the total amount thereof is preferably within the above range.

[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention so that they are localized on the surface of the photosensitive resin composition during the drying process after coating.

Furthermore, the higher fatty acid derivatives may also include compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass % relative to the total solid content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be only one kind or may be two or more kinds. When there are two or more kinds of higher fatty acid derivatives, it is preferred that their total is within the above range. [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like. The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. A large amount of inorganic particles may deteriorate the mechanical properties of the cured film. If the average particle size of the inorganic particles is greater than 2.0 μm, the resolution may decrease due to scattering of the exposure light. [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris(III)-based can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-butylphenyl salicylate, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc. Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, as examples of tribasic ultraviolet absorbers, there are 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tribasic, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium and other mono(hydroxyphenyl)trisinium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, Bis(hydroxyphenyl)triol compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triol, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triol; 2,4-bis(2-hydroxy-4- Tris(hydroxyphenyl)tris(iota) compounds such as 2,4-dibutoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(iota), 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(iota), and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(iota). In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but when contained, the content of the ultraviolet absorber is preferably 0.001 mass % or more and 1 mass % or less, and more preferably 0.01 mass % or more and 0.1 mass % or less, relative to the total solid content mass of the composition of the present invention. [Organic titanium compound] The resin composition of the present embodiment may contain an organic titanium compound. By containing an organic titanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when hardened at a low temperature. As organic titanium compounds that can be used, those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond can be cited. Specific examples of organic titanium compounds are shown in the following I) to VII). I) Titanium chelate compounds: Among them, titanium chelate compounds having two or more alkoxy groups are more preferred, considering that the negative photosensitive resin composition has excellent storage stability and can obtain a good hardened pattern. Specific examples are titanium bis(triethanolamine)diisopropoxytitanium, di(n-butoxy)bis(2,4-pentanedioate)titanium, diisopropoxybis(2,4-pentanedioate)titanium, diisopropoxybis(tetramethylpimelate)titanium, diisopropoxybis(ethyl acetylacetate)titanium, etc. II) Tetraalkoxytitanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetrakis[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanium cyclopentadiene compounds: for example, pentamethylcyclopentadiene trimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: for example, tri(dioctyl phosphate)isopropoxytitanium, tri(dodecyl benzenesulfonate)isopropoxytitanium, etc. V) Titanium oxide compounds: for example, bis(glutarate) oxide, bis(tetramethylpimelate) oxide, phthalocyanine oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc. Among them, as an organic titanium compound, from the perspective of exerting better drug resistance, at least one compound selected from the group including I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, diisopropoxybis(ethyl acetylacetate)titanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred. When an organic titanium compound is added, its amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern shows good heat resistance and chemical resistance. On the other hand, when the amount is 10 parts by mass or less, the storage stability of the composition is excellent. [Antioxidant] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the ductility characteristics of the film after hardening and the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As preferred phenolic compounds, hindered phenolic compounds can be cited. Compounds having a substituent at a position adjacent to a phenolic hydroxyl group (adjacent position) are preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as an antioxidant, a compound having a phenol group and a phosphite group in the same molecule is also preferred. In addition, as an antioxidant, a phosphorus-based antioxidant can also be preferably used. As the phosphorus-based antioxidant, there can be mentioned tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, and the like. As commercially available antioxidants, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION) and the like can be cited. In addition, as antioxidants, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, compounds in which the site that functions as an antioxidant is protected by a protecting group can be cited, and in which the protecting group is removed by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst, thereby functioning as an antioxidant. As potential antioxidants, compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219 can be cited. As commercially available products of potential antioxidants, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited. As examples of preferred antioxidants, there can be cited 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the following general formula (3). [Chemical Formula 54-3] In the general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and ^R6 represents an alkylene group having 2 or more carbon atoms. ^R7 represents an alkylene group having 2 or more carbon atoms and a monovalent to tetravalent organic group containing at least one selected from an O atom and a N atom. k represents an integer of 1 to 4. The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, by the anti-rust effect on metal materials, metal oxidation can be inhibited. In order to be able to act on both the resin and the metal material, it is more preferable that k is an integer of 2 to 4. As R ⁷ , there can be mentioned 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, -O-, -NH-, -NHNH-, combinations thereof, etc., which may further have a substituent. Among them, from the viewpoint of solubility in a developer and metal adhesion, an alkyl ether group or -NH- is preferred, and from the viewpoint of interaction with a resin and metal adhesion based on metal complex formation, -NH- is more preferred. The compounds represented by the following general formula (3) can be exemplified by the following compounds, but are not limited to the following structures. [Chemical Formula 54-4] [Chemical formula 54-5] [Chemical formula 54-6] [Chemical formula 54-7] The amount of antioxidant added is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, relative to the resin. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the ductility characteristics of the cured film and the effect of improving the adhesion to metal materials. When the amount added is more than 10 parts by weight, the sensitivity of the resin composition may decrease due to the interaction with the photosensitive agent. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

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

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

Furthermore, as a method for reducing metal impurities accidentally contained in the photosensitive resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the photosensitive resin composition of the present invention, filtering the raw material constituting the photosensitive resin composition of the present invention with a filter, lining the inside of a device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, the content of halogen atoms in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

As a container for storing the photosensitive resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials and the photosensitive resin composition, it is also preferable to use a multi-layer bottle having an inner wall of the container composed of six types of six layers of resins or a bottle having a seven-layer structure formed of six types of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

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

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

Furthermore, for the purpose of removing foreign matter such as dust or particles in the photosensitive resin composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. On the other hand, from the perspective of productivity, 5 μm or less is more preferred, 3 μm or less is more preferred, and 1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be used after being pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can be used in parallel or in series. When using multiple filters, 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 cycle filtering. In addition, filtering can be performed after pressurization. When filtering after pressurization, the pressure of pressurization is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the perspective of productivity, 0.01MPa or more and 1.0MPa or less is better, 0.03MPa or more and 0.9MPa or less is better, and 0.05MPa or more and 0.7MPa or less is even better. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filter filtering and impurity removal using an adsorbent can also be combined. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited. [Example]

The present invention is further described in detail below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose 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 based on mass.

<Synthesis Example 1> [Synthesis of polyimide precursor PIP-1] In a dry reactor equipped with a stirrer, a condenser and a flat-bottomed joint with an internal thermometer, 9.49 g (32.25 mmol) of 4,4'-diphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were added successively and stirred at 60°C for 18 hours. Next, the mixture was cooled to -20°C, and 16.1 g (135.5 mmol) of sulfinyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was warmed to room temperature, stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent solution. Next, 5.6 g (17.5 mmol) of methane and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45° C. under reduced pressure for 3 days, thereby obtaining polyimide precursor PIP-1.

<Synthesis Example 2> [Synthesis of polyimide precursor PIP-2] In the above-mentioned Synthesis Example 1, except that 4,4'-diaminodiphenyl ether was replaced with an equimolar amount of 1,6-diaminohexane, the polyimide precursor PIP-2 was obtained in the same manner as in Synthesis Example 1.

<Synthesis Example 3> [Synthesis of polyimide precursor PIP-3] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (4,4'-oxydiphthalic acid dried at 140°C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine and 140 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at -10±4°C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23°C over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 night. Next, 5 liters of water were added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was filtered, put into 4 liters of water and stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45° C. under reduced pressure for 3 days to obtain polyimide precursor PIP-3.

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

<Synthesis Example 5> [Synthesis of polybenzoxazole precursor PBP-1] Into a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 73.25 g (0.200 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.), 31.64 g (0.400 mol) of pyridine, and 293 g of NMP were added. The mixture was stirred at room temperature and then cooled to -15°C in a dry ice/methanol bath. While maintaining the reaction temperature at -5°C to -15°C, 30.11 g (0.144 mol) of a 30% by mass NMP solution of 1,4-cyclohexanedicarboxylic acid dichloride, 3.83 g (0.016 mol) of butylated chlorine (manufactured by Tokyo Chemical Industry Co., Ltd.), and a mixed solution of 96.25 g of NMP were added dropwise to the solution. After the addition, the obtained mixture was stirred at room temperature for 16 hours. Then, the reaction solution was cooled to below -5°C in an ice/methanol bath, and while maintaining the reaction temperature below -0°C, a mixed solution of 9.59 g (0.090 mol) of butylated chlorine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34.5 g of NMP was added dropwise. After the addition was completed, the mixture was further stirred for 16 hours. The reaction solution was diluted with 550 g of NMP and added to a 4 L mixture of deionized water/methanol (80/20 by volume) under vigorous stirring. The precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was vacuum dried at 50°C for 2 days to obtain resin A-1a. 25.00 g of resin A-1a, 125 g of NMP and 125 g of methyl ethyl ketone were added to a 500 mL eggplant-shaped flask and concentrated under reduced pressure at 60°C until the content became 160 g. 0.43 g (1.85 mmol) of camphorsulfonic acid (Tokyo Chemical Industry Co., Ltd.) and 5.12 g (0.065 mol) of 2,3-dihydrofuran (Wako Pure Chemical Industries, Ltd.) were added thereto, and stirred at room temperature for 1.5 hours. 0.37 g of triethylamine and 150 g of NMP were added to the obtained solution, and diluted. The obtained solution was poured into a 2 L deionized water/methanol (80/20 volume ratio) mixture that was stirred vigorously, and the precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was vacuum dried at 50°C for 2 days, thereby obtaining polybenzoxazole (PBO) precursor PBP-1.

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

[Table 1] Embodiment 1 2 3 4 5 6 7 8 Composition Resin Type PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 Quality 80 80 80 80 80 80 80 80 Free radical crosslinking agent Type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 7 7 7 7 7 7 7 7 Type - - - - - - - - Quality - - - - - - - - Photosensitizer Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 3 3 3 3 3 3 3 3 Silane coupling agent Type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 1 1 1 1 1 1 1 1 Type D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 Quality 1 1 1 1 1 1 1 1 Polymerization inhibitor Type E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Type E-3 E-3 E-3 E-3 E-3 E-3 E-3 E-3 Quality 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sensitizer Type F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Quality 2 2 2 2 2 2 2 2 Type F-2 F-2 F-2 F-2 F-2 F-2 F-2 F-2 Quality 5 5 5 5 5 5 5 5 Migration inhibitors Type - - - - - - - - Quality - - - - - - - - Acid crosslinking agent Type - - - - - - - - Quality - - - - - - - - Thermal acid generator Type - - - - - - - - Quality - - - - - - - - Additives Type - - - - - - - - Quality - - - - - - - - Thermoalkali generator Type - - - - - - - - Quality - - - - - - - - Surfactant Type - - - - - - - - Quality - - - - - - - - Solvent Type S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 ratio 80 80 80 80 80 80 80 80 Type S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 ratio 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 355 355 355 355 355 355 355 375 Impressions Fourfold Double Seventh level Fourfold Fourfold Fourfold Fourfold Fourfold Interval (seconds) 10 each 10 10 each 20 each 5/10/15 10 each 10 each 10 each Laser output (W) 0.6 0.6 0.6 0.6 0.6 1.2 1.8 0.6 Developer A A A A A A A A Hardening temperature (℃) 230 230 230 230 230 230 230 230 Hardening time (min) 120 120 120 120 120 120 120 120 Reviews Pattern shape evaluation A B A A A A A A Resolution evaluation A B A A A A B A

[Table 2] Embodiment 9 10 11 12 13 14 15 16 Composition Resin Type PIP-1 PI-1 PBP-1 PIP-1 PIP-2 PIP-3 PIP-1 PIP-1 Quality 80 54 100 80 80 32 80 80 Free radical crosslinking agent Type B-1 B-2 B-1 B-1 B-4 B-2 B-1 Quality 7 3 7 7 6.88 7 7 Type - B-3 - - - - - - Quality - 28 - - - - - - Photosensitizer Type C-1 C-3 C-4 C-1 C-1 C-1 C-1 C-2 Quality 3 5 3 3 3 1.04 3 3 Silane coupling agent Type D-1 D-3 D-5 D-1 D-1 D-4 D-1 D-1 Quality 1 1 3 1 1 0.70 1 1 Type D-2 - - D-2 D-2 - D-2 D-2 Quality 1 - - 1 1 - 1 1 Polymerization inhibitor Type E-1 E-4 - E-1 E-1 E-5 E-1 E-1 Quality 0.2 0.02 - 0.2 0.2 0.08 0.2 0.2 Type E-3 - - E-3 E-3 - E-3 E-3 Quality 0.5 - - 0.5 0.5 - 0.5 0.5 Sensitizer Type F-1 - - F-1 F-1 - F-1 F-1 Quality 2 - - 2 2 - 2 2 Type F-2 - - F-2 F-2 - F-2 F-2 Quality 5 - - 5 5 - 5 5 Migration inhibitors Type - - - - - G-1 - - Quality - - - - - 0.12 - - Acid crosslinking agent Type - H-1 - - - - - - Quality - 9 - - - - - - Thermal acid generator Type - I-1 - - - - - - Quality - 3 - - - - - - Additives Type - J-1 - - - - - - Quality - 1 - - - - - - Thermoalkali generator Type - - - - - K-1 - - Quality - - - - - 1.0 - - Surfactant Type - - L-1 - - - - - Quality - - 0.2 - - - - - Solvent Type S-1 S-3 S-1 S-1 S-1 S-1 S-1 S-1 ratio 80 80 100 80 80 80 80 80 Type S-2 S-4 - S-2 S-2 S-4 S-2 S-2 ratio 20 20 - 20 20 20 20 20 Solid content concentration 42 42 42 42 42 twenty one 42 42 Process Film thickness (μm) 20 20 20 30 20 20 20 20 Exposure wavelength (nm) 405 355 355 355 355 355 355 355 Impressions Fourfold Fourfold Fourfold Fourfold Fourfold Fourfold Fourfold Fourfold Interval (seconds) 10 each 10 each 10 each 10 each 10 each 10 each 10 each 10 each Laser output (W) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Developer A B B A A A A A Hardening temperature (℃) 230 230 230 230 230 230 230 230 Hardening time (min) 120 120 120 120 120 120 120 120 Reviews Pattern shape evaluation A B B A A A A A Resolution evaluation A A A A B A A A

[Table 3] Embodiment Comparison Example 17 18 19 20 twenty one twenty two twenty three 1 Composition Resin Type PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 PIP-1 Quality 80 80 80 80 80 80 80 80 Free radical crosslinking agent Type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 7 7 7 7 7 7 7 7 Type - - - - - - - - Quality - - - - - - - - Photosensitizer Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 3 3 3 3 3 3 3 3 Silane coupling agent Type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 2 1 1 1 1 1 1 1 Type - D-2 D-2 D-2 D-2 D-2 D-2 D-2 Quality - 1 1 1 1 1 1 1 Polymerization inhibitor Type E-1 MEHQ E-1 E-1 E-1 E-1 E-1 E-1 Quality 0.2 0.3 0.2 0.2 0.2 0.2 0.2 0.2 Type E-3 - E-3 E-3 E-3 E-3 E-3 E-3 Quality 0.5 - 0.5 0.5 0.5 0.5 0.5 0.5 Sensitizer Type F-1 F-1 - F-1 F-1 F-1 F-1 F-1 Quality 2 2 - 2 2 2 2 2 Type F-2 F-2 F-2 F-2 F-2 F-2 F-2 F-2 Quality 5 5 5 5 5 5 5 5 Migration inhibitors Type - - G-1 - - - - - Quality - - 1 - - - - - Acid crosslinking agent Type - - - - - - - - Quality - - - - - - - - Thermal acid generator Type - - - - - - - - Quality - - - - - - - - Additives Type - - - - - - - - Quality - - - - - - - - Thermoalkali generator Type - - - - - - - - Quality - - - - - - - - Surfactant Type - - - - - - - - Quality - - - - - - - - Solvent Type S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 ratio 80 80 80 80 80 80 80 80 Type S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 ratio 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 10 20 Exposure wavelength (nm) 355 355 355 355 355 HP 355 355 Impressions Fourfold Fourfold Fourfold Fourfold Fourfold Fourfold Fourfold Single Interval (seconds) 10 each 10 each 10 each 10 each 10 each 10 each 10 each - Laser output (W) 0.6 0.6 0.6 0.6/1.2 /1.8/1.8 0.6 - 0.6 0.6 Developer A A A A A A A A Hardening temperature (℃) 230 230 230 230 190 230 230 230 Hardening time (min) 120 120 120 120 120 120 120 120 Reviews Pattern shape evaluation A A A A A B A C Resolution evaluation A A A A A B A C

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

[Resin] ・PIP-1～PIP-3: PIP-1～PIP-3 synthesized in the above ・PI-1: PI-1 synthesized in the above ・PBP-1: PBP-1 synthesized in the above

[Free Radical Crosslinking Agent] ・B-1: Tetraethylene glycol dimethacrylate ・B-2: Dipentatriol hexaacrylate ・B-3: LIGHT ESTER BP-6EM (manufactured by KYOEISHA CHEMICAL Co., LTD.) ・B-4: SR209 (manufactured by Sartomer Japan Inc.)

[Photosensitive agent] ・C-1: Irgacure 784 (manufactured by BASF) ・C-2: Irgacure OXE-01 (manufactured by BASF) ・C-3: ADEKA NCI-930 (manufactured by ADEKA CORPORATION) ・C-4: Compound having the following structure [Chemical formula 55]

[Silane coupling agent] ・D-1: N-(3-(triethoxysilyl)propyl)-1,2-dimethoxybenzoic acid ・D-2: Benzophenone-3,3'-bis(N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic acid ・D-3: IM-1000 (manufactured by JX Nippon Mining & Metals Corporation) ・D-4: N-[3-(triethoxysilyl)propyl]butenedioic acid monoamide ・D-5: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Polymerization inhibitor] ・E-1: 2-nitroso-1-naphthol ・E-2: 4-methoxyphenol ・E-3: Compound with the following structure ・E-4: 4-methoxy-1-naphthol ・E-5: p-Benzoquinone [chemical formula 56]

[Sensitizer] ・F-1: 7-(Diethylamino)coumarin-3-carboxylic acid ethyl ester ・F-2: N-phenyldiethanolamine

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

[Acid crosslinking agent (other crosslinking agents)] ・H-1: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD.)

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

[Additives] ・J-1: 1,3-Dibutylthiourea

[Thermoalkali generator] ・K-1: Compound with the following structure [Chemical formula 57]

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

[Solvent] ・S-1: N-methyl-2-pyrrolidone ・S-2: Ethyl lactate ・S-3: γ-butyrolactone ・S-4: Dimethyl sulfoxide In Tables 1 to 3, the "Ratio" column indicates the content (mass %) of each solvent relative to the total mass of the solvent.

<Evaluation> [Evaluation of pattern shape] In each of the embodiments and comparative examples, each photosensitive resin composition or comparative composition was applied (coated) in layers on a silicon wafer by spin coating, thereby forming each photosensitive film. In each of the embodiments and comparative examples, the silicon wafer using the above-mentioned photosensitive film was dried on a heating plate at 80°C for 3 minutes, thereby forming a photosensitive film having a thickness described in the "Film Thickness (μm)" column of Tables 1 to 3 on the silicon wafer. The photosensitive film on the formed silicon wafer was exposed using a semiconductor laser having a laser output described in the "Laser Output (W)" column and an exposure wavelength described in the "Exposure Wavelength (nm)" column of Tables 1 to 3. For example, in Example 1, a total of 4 exposures were performed with a laser output of 0.6W. In Example 20, the first area exposure process was performed with an output of 0.6W, the second area exposure process was performed with an output of 1.2W, the third area exposure process was performed with an output of 1.8W, and the fourth area exposure process was performed with an output of 1.8W. In the example where "HP" is recorded in the "Exposure wavelength (nm)" column, exposure was performed using a high-pressure mercury lamp. Regarding exposure, exposure was performed with the number of times recorded in the "Exposure times" column of Tables 1 to 3 and the interval recorded in the "Interval (seconds)". For example, in Example 1, a total of 4 exposures (4-fold exposure) were performed at intervals of 10 seconds each (time when no exposure was performed). In Example 5, the exposure was performed 4 times in total while changing the interval to 5 seconds, 10 seconds, and 15 seconds. In each example or comparative example, each exposure process was performed with the same exposure amount. In addition, when a high-pressure mercury lamp was used for exposure, the above exposure amount was used as the exposure amount of i-ray. The exposure was performed through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 20μm). After the above exposure, in the example recorded as "A" in the "Developer" column of Tables 1 to 3, cyclopentanone was used for 60 seconds of development and propylene glycol monomethyl ether acetate (PGMEA) was used for 20 seconds to obtain the line and space pattern of the photosensitive film. In the example recorded as "B" in the "Developer" column of Tables 1 to 3, a 2.5 mass% tetramethylammonium hydroxide aqueous solution was used for 60 seconds for development and rinsed with pure water for 20 seconds, thereby obtaining the line and space pattern of the photosensitive film after exposure. In Example 11, the above development was performed after heating on a heating plate at 100°C/60 seconds. Thereafter, the above-developed pattern and the silicon wafer formed with the above pattern were heated at a heating rate of 10°C/minute in a nitrogen atmosphere, and after reaching the temperature recorded in the "Curing Temperature (°C)" column of Tables 1 to 3, the time recorded in the "Curing Time (min)" column of Tables 1 to 3 was maintained for curing, thereby obtaining a silicon wafer formed with a pattern. The silicon wafer on which the obtained pattern (line and space pattern) was formed was cut perpendicularly to the line and space pattern to expose the pattern cross section. The pattern cross section of the line and space pattern was observed at a magnification of 200 times using an optical microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, in each embodiment and comparative example, the taper angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the pattern was measured, and the evaluation was performed according to the following evaluation criteria. It can be said that the closer the taper angle is to 90°, the better the pattern shape is. -Evaluation Criteria- A: The taper angle is greater than 85° and less than 95°. B: The taper angle is greater than 80° and less than 85° or greater than 95° and less than 100°. C: The cone angle is less than 80° or greater than 100°.

[Resolution evaluation] In each embodiment and comparative example, a photosensitive film having a thickness described in the "Film Thickness (μm)" column of Tables 1 to 3 was formed on a silicon wafer in the same manner as in the pattern shape evaluation. As a photomask, a photomask having a line and space pattern with a scale of 1 μm between 5 μm and 25 μm was used, and the photosensitive film formed on the silicon wafer was exposed in the same manner as in the pattern shape evaluation. After the exposure, each photosensitive film was developed and heated in the same manner as in the pattern shape evaluation, thereby obtaining a silicon wafer having a pattern formed thereon. The pattern after the development was observed using a scanning electron microscope (SEM), and the minimum line width was determined. The evaluation was conducted according to the following evaluation criteria, and the evaluation results are shown in Tables 1 to 3. It can be said that the smaller the minimum line width is, the better the resolution is.

-Evaluation Criteria- A: Minimum line width less than 10μm B: Minimum line width greater than 10μm and less than 20μm C: Failure to obtain a pattern with a minimum line width greater than 20μm or with line width (with edge sharpness).

The pattern forming method of Comparative Example 1 performs only one exposure and does not have a second exposure process. In this example, it can be seen that the pattern shape is not good.

<Example 101> The photosensitive resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by spin coating, and dried at 80°C for 3 minutes to form a photocurable layer with a film thickness of 20μm. Then, a semiconductor laser with a laser output of 0.6W was used to expose a total of 4 times at intervals of 10 seconds each (time without exposure). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, development was performed with cyclopentanone for 60 seconds and rinsing was performed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds to obtain a layer pattern. Then, in a nitrogen atmosphere, the temperature was raised at a rate of 10°C/min. After reaching 230°C, it was maintained for 120 minutes to harden, thereby forming an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, the results of manufacturing semiconductor components using the interlayer insulating film for the redistribution layer confirmed normal operation.

without.

without.

Claims (13)

A pattern forming method includes: a first area exposure process, which is to selectively expose a part of a photosensitive film composed of a photosensitive resin composition, namely a first area; a second area exposure process, which is to selectively expose a part of the photosensitive film after the first area exposure process, namely a second area; and a developing process, which is to develop the photosensitive film after the second area exposure process, wherein at least a part of the area included in the first area and at least a part of the area included in the second area are a common area, and the photosensitive resin composition includes a polyimide, a polyimide precursor, a polybenzoic acid, a polyimide precursor, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid, a polybenzoic acid,

Azoles and polybenzo

At least one resin in the group of azole precursors and a photosensitive agent, including in a process of exposing a portion of the photosensitive film before the aforementioned developing process, the time from the end of a certain exposure process to the start of another exposure process and excluding the time of other exposure processes is more than 0.1 second. The pattern forming method as described in claim 1 includes: a third area exposure process, which is to selectively expose a part of the photosensitive film after the second area exposure process, namely the third area; and a fourth area exposure process, which is to selectively expose a part of the photosensitive film after the third area exposure process, namely the fourth area, and the developing process is a process for developing the photosensitive film after the fourth area exposure process, at least a part of the area included in the third area and at least a part of the area included in any one of the first area, the second area and the fourth area are a common area, and at least a part of the area included in the fourth area and at least a part of the area included in any one of the first area, the second area and the third area are a common area. The pattern forming method as described in claim 1 or claim 2, wherein the exposure wavelength in the aforementioned first area exposure process and the aforementioned second area exposure process is 300~450nm. A pattern forming method as described in claim 1 or claim 2, wherein the thickness of the photosensitive film formed by the aforementioned photosensitive resin composition is greater than 10 μm. A pattern forming method as described in claim 1 or claim 2, wherein an organic solvent is used as a developer to perform development in the aforementioned development process. The pattern forming method as described in claim 1 or claim 2, wherein the area of the area included in both the aforementioned first area and the aforementioned second area is 50% to 100% relative to the total area of the aforementioned first area. The pattern forming method as described in claim 1 or claim 2, wherein the aforementioned resin is a polyimide precursor. A pattern forming method as described in claim 1 or claim 2, wherein the aforementioned resin has a free radical polymerizable group. A pattern forming method as described in claim 1 or claim 2, wherein the aforementioned photosensitive resin composition further comprises a free radical crosslinking agent. The pattern forming method as described in claim 1 or claim 2, wherein the aforementioned photosensitive resin composition further comprises a sensitizer. A photosensitive resin composition is used to form the aforementioned photosensitive film in the pattern forming method described in any one of claim 1 to claim 10. A method for manufacturing a laminate, comprising a pattern forming method as described in any one of claims 1 to 10. A method for manufacturing an electronic component, comprising the pattern forming method described in any one of claim 1 to claim 10 or the method for manufacturing a laminate described in claim 12.