Pattern forming method, photosensitive resin composition, method for producing laminated body, and method for producing semiconductor device

Abstract

The present invention provides a pattern forming method in which the resulting pattern has an excellent shape, a photosensitive resin composition used in the pattern forming method, a method for producing a laminated body using the pattern forming method, and a method for producing an electronic device using the pattern forming method. The pattern forming method includes: a first region exposure step of selectively exposing a first region, a portion of a photosensitive film composed of the photosensitive resin composition; a second region exposure step of selectively exposing the second region; and a development step of developing the photosensitive film after the second region exposure step. At least a portion of the first region and at least a portion of the second region are common regions. The photosensitive resin composition contains a specific resin and a photosensitizer.

Description

Technical Field

[0001] The present invention relates to a pattern forming method, a photosensitive resin composition, a method for producing a laminate, and a method for producing a semiconductor device. Background Art

[0002] Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulation properties, making them useful in a variety of applications. While these applications are not particularly limited, using semiconductor devices for mounting as an example, patterns containing these resins can be used as insulating films, sealing materials, or protective films. Furthermore, patterns containing these resins are also used as base films or cover films for flexible substrates.

[0003] For example, in the above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of a photosensitive resin composition containing these resins or their precursors.

[0004] For example, such a photosensitive resin composition is applied to a substrate by coating or the like, and then subjected to exposure, development, heating, etc. as needed, thereby forming a cured resin on the substrate.

[0005] Photosensitive resin compositions can be applied using known coating methods, allowing for greater freedom in designing the shape, size, and application location of the applied photosensitive resin composition. This superior manufacturing adaptability, in addition to the high performance of polyimides and polybenzoxazoles, is driving increasing expectations for the expansion of industrial applications of photosensitive resin compositions containing these resins.

[0006] 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 quinone diazo is exposed, developed, and patterned, and then subjected to overall exposure and curing.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 9-146273 Summary of the Invention

[0010] Technical issues to be solved by the invention

[0011] Conventionally, a photosensitive resin composition containing polyimide or polybenzoxazole or a precursor thereof is applied to a substrate, exposed and developed, and then heated as needed to form a pattern.

[0012] In the formation of the above-mentioned pattern, it is desired to provide a pattern forming method in which the obtained pattern has an excellent shape.

[0013] An 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 pattern forming method, a method for producing a laminated body using the pattern forming method, and a method for producing an electronic device using the pattern forming method.

[0014] Means for solving technical problems

[0015] Hereinafter, examples of representative embodiments of the present invention will be described.

[0016] <1> A pattern forming method comprising:

[0017] A first region exposure step of selectively exposing a first region, which is a portion of the photosensitive film formed of the photosensitive resin composition;

[0018] A second area exposure step of selectively exposing a portion of the photosensitive film after the first area exposure step, namely, a second area; and

[0019] A developing step is to develop the photosensitive film after the second area exposure step.

[0020] At least a portion of the area included in the first area and at least a portion of the area included in the second area are a common area.

[0021] The photosensitive resin composition includes at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor, and a photosensitizer.

[0022] <2> The pattern forming method according to <1>, comprising:

[0023] A third area exposure step of selectively exposing a portion of the photosensitive film after the second area exposure step, namely, a third area; and

[0024] The fourth area exposure step is to selectively expose a portion of the photosensitive film after the third area exposure step, i.e., the fourth area.

[0025] The above-mentioned development process is a process for developing the photosensitive film after the exposure process of the above-mentioned fourth area, and at least a portion of the area included in the above-mentioned third area and at least a portion of the area included in any one of the above-mentioned first area, the above-mentioned second area and the above-mentioned fourth area are a common area, and at least a portion of the area included in the above-mentioned fourth area and at least a portion of the area included in any one of the above-mentioned first area, the above-mentioned second area and the above-mentioned third area are a common area.

[0026] <3> The pattern forming method according to <1> or <2>, wherein

[0027] In the process of exposing a partial region of the photosensitive film before the development process, the time from the end of a certain exposure process to the start of another exposure process excluding the other exposure processes is 0.1 seconds or longer.

[0028] <4> The pattern forming method according to any one of <1> to <3>, wherein

[0029] The exposure wavelength in the first region exposure step and the second region exposure step is 300 nm to 450 nm.

[0030] <5> The pattern forming method according to any one of <1> to <4>, wherein

[0031] The photosensitive film composed of the photosensitive resin composition has a thickness of 10 μm or more.

[0032] <6> The pattern forming method according to any one of <1> to <5>, wherein

[0033] The development in the above-mentioned development step is performed using an organic solvent as a developer.

[0034] <7> The pattern forming method according to any one of <1> to <6>, wherein

[0035] The ratio of the area of ​​the region included in both the first region and the second region to the total area of ​​the first region is 50% to 100%.

[0036] <8> The pattern forming method according to any one of <1> to <7>, wherein

[0037] The above resin is a polyimide precursor.

[0038] <9> The pattern forming method according to any one of <1> to <8>, wherein

[0039] The above resin has a radical polymerizable group.

[0040] <10> The pattern forming method according to any one of <1> to <9>, wherein

[0041] The photosensitive resin composition further includes a radical crosslinking agent.

[0042] <11> The pattern forming method according to any one of <1> to <10>, wherein

[0043] The photosensitive resin composition further contains a sensitizer.

[0044] <12> A photosensitive resin composition for forming the photosensitive film in the pattern forming method according to any one of <1> to <11>.

[0045] <13> A method for producing a laminate, comprising the pattern forming method according to any one of <1> to <11>.

[0046] <14> A method for manufacturing an electronic device, comprising the pattern forming method according to any one of <1> to <11> or the method for manufacturing a laminate according to <13>.

[0047] Effects of the Invention

[0048] According to the present invention, there are provided a pattern forming method in which the obtained pattern has an excellent shape, a photosensitive resin composition used in the pattern forming method, a method for producing a laminated body using the pattern forming method, and a method for producing an electronic device using the pattern forming method. DETAILED DESCRIPTION

[0049] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0050] In this specification, the numerical range expressed by the symbol “to” indicates a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0051] The term "step" in this specification refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the desired effect of the step can be achieved.

[0052] Regarding the marking of groups (atomic groups) in this specification, the markings not indicating substitution and unsubstituted include both groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0053] In this specification, "exposure" includes, unless otherwise specified, exposure using light as well as exposure using a particle beam such as an electron beam or an ion beam. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.

[0054] 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)acryloyl” means both or either of “acryloyl” and “methacryloyl”.

[0055] In the present 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.

[0056] In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total components of the composition. In addition, the solid content concentration in this specification refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0057] In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are based on gel permeation chromatography (GPC determination) and are defined as polystyrene conversion values. In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained using HLC-8220GPC (TOSOH CORPORATION system) and protective column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel SuperHZ2000 (TOSOH CORPORATION system) as a column. Unless otherwise specified, these molecular weights are set to the molecular weight measured using THF (tetrahydrofuran) as an eluent. Furthermore, unless otherwise specified, the detection in the GPC determination uses a wavelength 254nm detector of UV line (ultraviolet rays).

[0058] In this specification, when the positional relationship of the layers constituting the laminate is described as "up" or "down", it is sufficient that other layers exist on the upper or lower side of the layer that serves as the reference in the multilayer of interest. That is, a third layer or a third element may be further sandwiched between the layer that serves as the reference and the above-mentioned other layers, and the layer that serves as the reference and the above-mentioned other layers do not need to be in contact. Furthermore, unless otherwise specified, the direction in which the layers are stacked relative to the substrate is referred to as "up", or when a photocurable layer is present, the direction from the substrate toward the photocurable layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of these upper and lower directions is for convenience in this specification. In actual practice, the "up" direction in this specification may also be different from the vertical direction.

[0059] In this specification, unless otherwise specified, each component contained in a composition may include two or more compounds that meet the requirements of the component. Furthermore, 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.

[0060] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0061] In this specification, a combination of preferred embodiments is considered a more preferred embodiment.

[0062] (Pattern Formation Method)

[0063] The pattern forming method of the present invention includes: a first area exposure step of selectively exposing a portion of a photosensitive film composed of a photosensitive resin composition, namely a first area; a second area exposure step of selectively exposing a portion of the photosensitive film after the first area exposure step, namely a second area; and a development step of developing the photosensitive film after the second area exposure step, wherein at least a portion of the area included in the first area and at least a portion of the area included in the second area are a common area, and the photosensitive resin composition includes at least one resin selected from polyimide, a polyimide precursor, polybenzoxazole and a polybenzoxazole precursor (hereinafter also referred to as "specific resin"), and a photosensitive agent.

[0064] The pattern obtained in the pattern forming method of the present invention has an excellent shape.

[0065] The mechanism by which the above effects are achieved is not yet clear, but can be speculated as follows.

[0066] Conventionally, a photosensitive film formed from a photosensitive resin composition containing polyimide, polybenzoxazole, or a precursor thereof and a photosensitizer is exposed and developed, and then heated as needed to form a pattern.

[0067] As a result of intensive research, the present inventors have found that by subjecting a photosensitive film formed from the photosensitive resin composition to the first and second region exposure steps, the shape of the pattern after exposure and development can be suppressed from being tapered or inverted tapered.

[0068] This is presumably because, by performing exposure in a divided manner into a first area exposure process and a second area exposure process rather than performing exposure in one time, the amount of free radicals, acids, etc. generated from the photosensitive agent due to one exposure can be reduced. As a result, the diffusion of the above-mentioned free radicals, acids, etc. in the photosensitive film is suppressed.

[0069] In the present invention, the angle formed by the surface of the substrate on which the pattern is formed and the side surface of the pattern is called the cone angle, the pattern shape when the cone angle is significantly less than 90° (for example, the cone angle is less than 80°, etc.) is called an inverted cone, and the pattern shape when the cone angle is significantly greater than 90° (for example, the cone angle exceeds 100°, etc.) is called a cone.

[0070] In the present invention, an excellent pattern shape means that the taper angle is close to 90°.

[0071] For example, when the photosensitive film is a negative-type photosensitive film, as described later, it is believed that the photosensitive agent is more susceptible to photosensitization due to the high energy of the exposure light in the portion of the photosensitive film on the side facing the exposure light source in the thickness direction of the photosensitive film, and thus is more susceptible to the generation of free radicals, acids, etc. Furthermore, it is believed that the photosensitive agent is less susceptible to photosensitization due to the weakened and weaker energy of the exposure light in the portion of the photosensitive film on the side opposite to the exposure light source in the thickness direction of the photosensitive film (e.g., on the substrate side), and thus is less susceptible to the generation of free radicals, acids, etc. As a result, the degree of curing of the composition differs between the exposure light source side and the substrate side of the photosensitive film, and it is believed that the pattern shape is more susceptible to an inverted cone.

[0072] Furthermore, when the photosensitive film is a positive-type photosensitive film, as described later, it is believed that the photosensitive agent is particularly susceptible to photosensitization, for example, acid generation, due to the high energy of the exposure light on the side of the photosensitive film in the thickness direction. Furthermore, it is believed that the photosensitive agent is less susceptible to photosensitization, for example, acid generation, due to the weakened and weaker energy of the exposure light on the side of the photosensitive film opposite to the exposure light in the thickness direction (for example, the substrate side). As a result, the solubility of the composition in the developer differs between the exposure light side and the substrate side of the photosensitive film, and it is believed that the pattern shape is more likely to be tapered.

[0073] When exposing such a negative photosensitive film or a positive photosensitive film by dividing the exposure into a first area exposure process and a second area exposure process, there is a time when no exposure is performed between the first area exposure process and the second area exposure process. Therefore, it is believed that the subsequent diffusion of free radicals, acids, etc. is suppressed, thereby suppressing the pattern shape from becoming an inverted cone or a cone.

[0074] Patent Document 1 neither describes nor suggests a pattern forming method including a first area exposure step and a second area exposure step.

[0075] Hereinafter, the pattern forming method of the present invention will be described in detail.

[0076] The pattern forming method of the present invention includes a first area exposure step and a second area exposure step.

[0077] Furthermore, the pattern forming method of the present invention may further include a third region exposure step, a fourth region exposure step, other exposure steps, and the like, which will be described later, in addition to the first region exposure step and the second region exposure step.

[0078] In the present invention, the first area exposure process, the second area exposure process, the third area exposure process, the fourth area exposure process, and other exposure processes including the exposure of the photosensitive film are also simply collectively referred to as "exposure process".

[0079] <First area exposure step>

[0080] The pattern forming method of the present invention includes a first area exposure step of exposing a portion of a photosensitive film composed of a photosensitive resin composition.

[0081] In the first area exposure step, a photosensitive agent described later is exposed to light, and the solubility of the photosensitive film in the developer changes.

[0082] Specifically, for example, when the photosensitizer is a photopolymerization initiator described later, polymerization proceeds in the photosensitive film, and the solubility of the photosensitive film in the developer after the first region step decreases.

[0083] Furthermore, for example, when the photosensitizer 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.

[0084] Furthermore, for example, when the photosensitizer 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.

[0085] As described above, in the first area exposure process, the photosensitivity of the photosensitive agent can be used to promote the bonding reaction between the cross-linking groups contained in the specific resin or cross-linking 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 products produced by the chemical changes based on the photosensitivity of the photosensitive agent.

[0086] That is, the photosensitive film in the present invention may be a positive photosensitive film or a negative photosensitive film.

[0087] A positive photosensitive film refers to a photosensitive film whose exposed portion (exposed portion) in the first area exposure process and the second area exposure process is removed by a developer, and a negative photosensitive film refers to a photosensitive film whose unexposed portion (non-exposed portion) in the above exposure process is removed by a developer.

[0088] In the present invention, a photosensitive film utilizing the catalytic action of an acid generated from a photosensitive agent by exposure is also referred to as a chemically amplified photosensitive film. The chemically amplified photosensitive film preferably comprises a resin having a polarity conversion group such as an acid-decomposable group and a photoacid generator.

[0089] The thickness of the photosensitive film is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, from the perspective of easily achieving the effects of the present invention. The upper limit of the thickness is not particularly limited, but is preferably 50 μm or less, more preferably 30 μm or less.

[0090] The exposure wavelength in the first area exposure step may be appropriately set as a wavelength to which a photosensitizer described later has sensitivity, and is preferably 190 to 580 nm, more preferably 240 to 550 nm, further preferably 300 to 450 nm, and particularly preferably 300 to 420 nm.

[0091] Regarding the exposure wavelength, if described in relation to the light source (exposure method), examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broad (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, and (7) second harmonics (wavelength 532 nm) and third harmonics (wavelength 355 nm) of YAG lasers. Regarding the photosensitive resin composition of the present invention, exposure using i-rays is preferred. This allows for particularly high exposure sensitivity. From the viewpoint of operability and productivity, a high-pressure mercury lamp with a broad wavelength (three wavelengths of g, h, and i rays) or a semiconductor laser of 405 nm is also preferred.

[0092] Furthermore, exposure using a laser light source such as a semiconductor laser is preferred because it does not require a mask pattern such as a photomask, and even if a mask pattern is used, the freedom of use is increased, it is easy to remove unnecessary wavelengths or it is easy to increase the exposure illuminance and shorten the exposure time, or it is possible to extend the life of the exposure light source.

[0093] Examples of a method for exposing a portion of the photosensitive film in the first region exposure step include an exposure method using a known photomask and an exposure method for exposing a portion of the photosensitive film by laser exposure or the like.

[0094] <Second area exposure step>

[0095] The pattern forming method of the present invention includes a second region exposure step performed after the first region exposure step to selectively expose a second region, which is a partial region of the photosensitive film after the first region exposure step.

[0096] The second region exposure step can be performed in the same manner as the first region exposure step, except that at least a portion of the region included in the first region and at least a portion of the region included in the second region are common regions.

[0097] The exposure wavelength in the second area exposure step may be appropriately set as a wavelength to which a photosensitizer described later has sensitivity, and is preferably 190 to 580 nm, more preferably 240 to 550 nm, further preferably 300 to 450 nm, and particularly preferably 300 to 420 nm.

[0098] Furthermore, the exposure wavelength in the second region exposure step may be the same as or different from the exposure wavelength in the first region exposure step, but is preferably the same as the exposure wavelength.

[0099] The exposure method in the second region exposure step is not particularly limited, and the same exposure method as that in the first region exposure step can be used.

[0100] Furthermore, the exposure method in the second region exposure step may be the same as or different from the exposure method in the first region exposure step, but is preferably the same.

[0101] The ratio of the area of ​​the region included in both the first region and the second region to the total area of ​​the first region is preferably 50 to 100%, more preferably 70 to 100%, further preferably 80 to 100%, and particularly preferably 90 to 100%.

[0102] Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention.

[0103] <Third Area Exposure Step, Fourth Area Exposure Step>

[0104] The pattern forming method of the present invention includes a third area exposure process of selectively exposing a portion of the photosensitive film after the second area exposure process, namely the third area. The development process is a process of developing the photosensitive film after the third area exposure process. Preferably, 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 and the second area are a common area.

[0105] Furthermore, the pattern forming method of the present invention includes a third area exposure process of selectively exposing a portion of the photosensitive film after the second area exposure process, namely, the third area, and a fourth area exposure process of selectively exposing a portion of the photosensitive film after the third area exposure process, namely, the fourth area. The development process is a process for developing the photosensitive film after the fourth area exposure process. Preferably, 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 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.

[0106] The third region exposure step and the fourth region exposure step can be performed by the same method as the first region exposure step described above.

[0107] Furthermore, the exposure wavelengths in the third region exposure step and the fourth region exposure step may be the same as or different from the exposure wavelength in the first region exposure step, but are preferably the same.

[0108] Furthermore, the exposure methods in the third region exposure step and the fourth region exposure step may be the same as or different from the exposure method in the first region exposure step, but are preferably the same.

[0109] The ratio of the area of ​​the area included in the above-mentioned third region and at least any one of the above-mentioned first region, the above-mentioned second region and the above-mentioned fourth region to the total area of ​​the above-mentioned third region is preferably 50 to 100%, more preferably 70 to 100%, further preferably 80 to 100%, and especially preferably 90 to 100%.

[0110] Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention.

[0111] The ratio of the area of ​​the area included in the above-mentioned fourth region and at least any one of the above-mentioned first region, the above-mentioned second region and the above-mentioned third region to the total area of ​​the above-mentioned fourth region is preferably 50 to 100%, more preferably 70 to 100%, further preferably 80 to 100%, and especially preferably 90 to 100%.

[0112] Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention.

[0113] <Other exposure processes>

[0114] The pattern forming method of the present invention may further include, after the fourth step, another exposure step other than the first region exposure step, the second region exposure step, the third region exposure step, and the fourth region exposure step.

[0115] The pattern forming method of the present invention includes another exposure process for selectively exposing a portion of the photosensitive film after the fourth region exposure process, i.e., another region. The development process is a process for developing the photosensitive film after the other exposure process. Preferably, at least a portion of the region included in the other region and at least a portion of the region included in any one of the first region, the second region, the third region, the fourth region and the other region in another other exposure process are common regions.

[0116] The other exposure steps can be performed by the same method as the first region exposure step described above.

[0117] Furthermore, the other exposure step may be a step of exposing the entire photosensitive film (global exposure) instead of exposing a portion of the photosensitive film composed of the photosensitive resin composition.

[0118] Furthermore, the exposure wavelength in the other exposure steps may be the same as or different from the exposure wavelength in the first region exposure step, but is preferably the same as the exposure wavelength.

[0119] Furthermore, the exposure methods in the other exposure steps may be the same as or different from the exposure method in the first region exposure step, but are preferably the same.

[0120] Regarding the process of 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, more preferably includes 3 to 8 times, and further preferably includes 4 to 7 times.

[0121] The ratio of the area of ​​the area included in the above-mentioned other areas and at least any one of the above-mentioned first area, the above-mentioned second area, the above-mentioned third area, the above-mentioned fourth area and other areas in another other exposure process to the total area of ​​the above-mentioned other areas is preferably 50 to 100%, more preferably 70 to 100%, further preferably 80 to 100%, and especially preferably 90 to 100%.

[0122] Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention.

[0123] Furthermore, the ratio of the total area of ​​the regions exposed twice or more contained in the photosensitive film to the total area of ​​the regions exposed at least once is preferably 50 to 100%, more preferably 70 to 100%, further preferably 80 to 100%, and particularly preferably 90 to 100%.

[0124] Setting the above ratio to 100% is also one of the preferred aspects of the pattern forming method of the present invention.

[0125] <Interval>

[0126] In the pattern forming method of the present invention, in the step of exposing a portion of the photosensitive film prior to the development step, the time from the completion of one exposure step to the start of another exposure step, excluding the other exposure steps, is preferably 0.1 seconds or longer, more preferably 0.5 seconds or longer, even more preferably 1 second or longer, and particularly preferably 5 seconds or longer. The upper limit of the above time is not particularly limited, and may be, for example, 24 hours or shorter.

[0127] In the present invention, the time from the end of a certain exposure process to the start of another exposure process, excluding the other exposure processes, is also referred to as an "interval."

[0128] It is considered that by providing the above-mentioned interval, diffusion of radicals, acids, etc. generated by photosensitization of the photosensitizer is suppressed, thereby achieving an excellent pattern shape.

[0129] For example, if the photosensitive film contains a crosslinking agent, etc., and its solubility in the developer changes due to crosslinking of the components in the photosensitive film (polymerization of a free radical crosslinking agent or crosslinking of another crosslinking agent), it is believed that crosslinking occurs during the above-mentioned interval, and the mobility of the field decreases. Therefore, it is believed that the diffusion of free radicals, acids, etc. generated when further exposure is performed after the interval is suppressed.

[0130] Furthermore, for example, when the photosensitive film is a specific resin containing a polarity-converting group such as an acid-degradable group, and its solubility in the developer changes due to structural changes such as deprotection of components in the photosensitive film, it is believed that the polarity of the field increases during the aforementioned interval, and the diffusivity of polar molecules decreases. Therefore, it is believed that the diffusion of acids, etc. generated during further exposure after the interval is suppressed.

[0131] As an example, when a total of four 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.

[0132] When the process includes exposing the photosensitive film three or more times, there may be multiple intervals between exposures, and these multiple intervals may be the same or different. Furthermore, when there are multiple intervals, at least one of these multiple intervals is preferably 0.1 seconds or longer, more preferably 0.5 seconds or longer, even more preferably 1 second or longer, and particularly preferably 5 seconds or longer. The upper limit of the interval is not particularly limited, and for example, it may be 24 hours or shorter.

[0133] For example, as another example, when a total of four 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.

[0134] Furthermore, conversely, when a total of four 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.

[0135] Exposure wavelength

[0136] In the above aspect, in the pattern forming method of the present invention, the exposure wavelength in the first region exposure step and the second region exposure step is preferably 300 to 450 nm, and more preferably 300 to 420 nm.

[0137] Furthermore, 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 to 450 nm, more preferably 300 to 420 nm.

[0138] Exposure

[0139] In the pattern forming method of the present invention, the exposure amount of the photosensitive film exposed in the first area exposure step, the second area exposure step, and the like (the total exposure amount of the photosensitive film based on multiple exposures such as the first area exposure step, the second area exposure step, and the third area exposure step) is preferably 100 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength to which the photosensitizer has sensitivity. 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0140] Furthermore, the focus positions in multiple exposures may be the same or different.

[0141] The exposure amount in each step such as the first area exposure step and the second area exposure step is not particularly limited. As long as the total is within the above-mentioned exposure amount range, the exposure amount in each step may be the same or different.

[0142] Furthermore, the exposure outputs in each step, such as the first and second area exposure steps, may be the same or different. For example, it is preferable to perform exposure in the second area exposure step at a higher exposure output than in the first area exposure step. When performing a total of four exposures from the first to fourth area exposure steps, it is also preferable to perform exposure at a high exposure output comparable to that of the subsequent steps.

[0143] <Post-exposure heating process>

[0144] The pattern forming method of the present invention may include a step of heating after exposure (post-exposure heating step).

[0145] The post-exposure heating process can be performed after the above-mentioned first area exposure process, second area exposure process and other exposure processes and before the development process. It can also be performed once each time the photosensitive film is exposed, such as once after the first area exposure process and once after the second area exposure process. It can also be determined whether to perform the post-exposure heating process each time the photosensitive film is exposed.

[0146] The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.

[0147] The heating time in the post-exposure heating step is preferably 1 minute to 300 minutes, more preferably 5 minutes to 120 minutes.

[0148] The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the heating start temperature to the maximum heating temperature.

[0149] Furthermore, the temperature increase rate can be appropriately changed during the heating period.

[0150] The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.

[0151] Furthermore, heating is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0152] <Film formation process>

[0153] The pattern forming method of the present invention may include a film forming step of forming a photosensitive film from the photosensitive resin composition.

[0154] The photosensitive film in the first region exposure step may be a photosensitive film formed in a film formation step or may be a photosensitive film obtained by a method such as purchasing.

[0155] The film-forming step is preferably a step of applying the photosensitive resin composition to a substrate to form a film (layer) to obtain a photosensitive film.

[0156] 〔Base material〕

[0157] The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited 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 (PDPs).

[0158] In the present invention, a semiconductor manufacturing substrate is particularly preferred, and a silicon substrate, a Cu substrate, and a mold substrate are more preferred.

[0159] Furthermore, layers such as an adhesion layer and an oxide layer may be provided on the surface of these substrates.

[0160] Furthermore, the shape of the substrate is not particularly limited and may be circular or rectangular.

[0161] On the surface of these substrates, a layer such as an adhesion layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided.

[0162] Furthermore, the shape of the substrate is not particularly limited and may be circular or rectangular.

[0163] The size of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in diameter if circular, and 100 to 1000 mm in length, preferably 200 to 700 mm in length, for example, in length of the short side of a rectangular substrate.

[0164] Furthermore, as the base material, for example, a plate-shaped base material (substrate) is used.

[0165] 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 serves as a base material.

[0166] As a method of applying the photosensitive resin composition to a substrate, coating is preferred.

[0167] Specifically, as applicable methods, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet methods can be exemplified. From the viewpoint of thickness uniformity of the photosensitive film, spin coating, slit coating, spray coating, and inkjet methods are more preferred, and from the viewpoint of easily obtaining the effects of the present invention, slit coating is preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a photosensitive film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, spin coating, spray coating, inkjet methods, etc. are preferred, and as long as it is a rectangular substrate, slit coating, spray coating, inkjet methods, etc. are preferred. In the case of the spin coating method, 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 desired film thickness, it is also preferred to apply the coating at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Furthermore, in order to obtain a uniform film thickness, a combination of multiple rotation speeds may be used for coating.

[0168] Furthermore, a method of transferring a coating film formed by applying the coating film in advance on a temporary support by the above-mentioned applying method onto a substrate can also be applied.

[0169] Regarding the transfer method, in the present invention, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably utilized.

[0170] Furthermore, a process for removing excess film from the edges of the substrate may be performed. Examples of such processes include edge bead removal (EBR), air knife, and backside washing. A pre-wetting process may also be employed: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve its wettability, and then the resin composition is applied.

[0171] <Drying process>

[0172] The pattern forming method of the present invention may include a step (drying step) of drying the formed film (layer) to remove the solvent after the film forming step (layer forming step).

[0173] The drying temperature is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

[0174] <Development Process>

[0175] The pattern forming method of the present invention includes a developing step of developing the exposed photosensitive film with a developer to obtain a pattern.

[0176] By developing, one of the exposed and unexposed areas is removed. The development method is not particularly limited as long as the desired pattern can be formed; examples include nozzle spraying, spraying, and immersing the substrate in the developer solution. Nozzle spraying is preferred. The development step can include a step of continuously supplying the developer solution to the substrate, a step of holding the substrate in a substantially stationary state, a step of vibrating the developer solution using ultrasound or other methods, or a combination of these.

[0177] Development is performed using a developer. As the developer, in the case of negative development, a developer that removes unexposed portions (non-exposed portions) can be used, and in the case of positive development, a developer that removes exposed portions (exposed portions) can be used, without particular limitation.

[0178] The development in the development step of the present invention is preferably performed using an organic solvent as a developer, and more preferably a developer containing 50% by mass or more of an organic solvent relative to the total mass of the developer.

[0179] Furthermore, the developer may contain a known surfactant.

[0180] In the present invention, the use of an alkali developer as a developer is referred to as alkali development, and the use of a developer containing 50% by mass or more of an organic solvent relative to the total mass of the developer as a developer is referred to as solvent development.

[0181] In alkali development, the developer preferably has an organic solvent content of 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably does not contain an organic solvent.

[0182] The developer in the alkali development is more preferably an aqueous solution having a pH of 10 to 15.

[0183] Examples of the alkali compound contained in the developer in alkali development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia, or amines. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH), or tetraethylammonium hydroxide. Among these, a metal-free alkali compound is preferred, and an ammonium compound is more preferred.

[0184] When TMAH is used as the alkaline compound, for example, the content of TMAH is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass relative to the total mass of the developer.

[0185] The base compound may be one or two or more. When the base compounds are two or more, the total amount thereof is preferably within the above range.

[0186] In solvent development, the developer preferably contains at least 90% of an organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, more preferably 0 to 3. The ClogP value can be calculated by inputting the structural formula into ChemBioDraw (chemical drawing software).

[0187] As the organic solvent, esters include, for example, 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 alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate), etc. )), 3-alkoxypropionic acid alkyl esters (e.g., 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (e.g., 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxypropionic acid alkyl esters (e.g., 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl ester, etc. (e.g., 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid propyl ester, etc.) ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like are preferably mentioned. Examples of the preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of the preferred aromatic hydrocarbons include toluene, xylene, anisole, and limonene; and examples of the preferred sulfoxides include dimethyl sulfoxide.

[0188] In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, one organic solvent may be used alone or in combination of two or more.

[0189] The developer may further contain other components. Examples of the other components include well-known surfactants and well-known defoaming agents.

[0190] [Developer Supply Method]

[0191] The method for supplying the developer is not particularly limited as long as the desired pattern can be formed. Examples include immersing the substrate in the developer, blanket development in which the developer is supplied onto the substrate using a nozzle, and continuous supply of the developer. The type of nozzle is not particularly limited, and examples include direct current nozzles, showerhead nozzles, and spray nozzles.

[0192] From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a direct current nozzle or a continuous supply method using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply the developer using a spray nozzle.

[0193] 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 spin drying, the developer is continuously supplied again with a DC nozzle, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times.

[0194] In addition, as a method for supplying the developer in the development process, a process of continuously supplying the developer on the substrate, a process of keeping the developer on the substrate in a roughly static state, a process of vibrating the developer on the substrate using ultrasonic waves, etc., and a combination of these processes can be adopted.

[0195] The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but can generally be 10 to 45°C, more preferably 20 to 40°C.

[0196] In the development step, rinsing may be further performed after the treatment with the developer, or a method such as supplying a rinsing liquid before the developer in contact with the pattern completely dries may be employed.

[0197] In the case of solvent development, it is preferred to perform rinsing with an organic solvent different from the developer.

[0198] In the case of alkali development, rinsing with pure water is preferred.

[0199] 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.

[0200] The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0201] When the rinsing liquid contains an organic solvent, the organic solvent includes, for example, 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 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., 3- Methyl alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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, 2-methoxy-2- methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Esters, 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.

[0202] When the rinse liquid contains an organic solvent, a single organic solvent or a mixture of two or more organic solvents may be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0203] When the rinsing liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Furthermore, the organic solvent may constitute 100% by mass of the rinsing liquid.

[0204] The rinsing solution may further comprise other ingredients.

[0205] Examples of other components include known surfactants and known defoaming agents.

[0206] [How to supply flushing fluid]

[0207] As long as the desired pattern can be formed, the method of supplying the rinsing liquid is not particularly limited. Examples include a method of immersing the substrate in the rinsing liquid, liquid coating development on the substrate, a method of supplying the rinsing liquid on the substrate using a shower head, and a method of continuously supplying the rinsing liquid on the substrate through a direct current nozzle.

[0208] From the perspectives of rinse liquid permeability, removal of non-image areas, and manufacturing efficiency, a method of supplying the rinse liquid using a shower nozzle, direct current nozzle, or spray nozzle is preferred, with continuous supply using a spray nozzle being more preferred. From the perspective of the rinse liquid's permeability to the image area, a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include direct current nozzles, shower nozzles, and spray nozzles.

[0209] That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film using a direct current nozzle or continuously supplying the rinsing liquid, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[0210] In addition, as a method for supplying the rinsing liquid in the rinsing process, a process of continuously supplying the rinsing liquid on the substrate, a process of keeping the rinsing liquid on the substrate in a roughly static state, a process of vibrating the rinsing liquid on the substrate using ultrasonic waves, etc., and a combination of these processes can be adopted.

[0211] <Heating process>

[0212] The production method of the present invention preferably includes a step of heating the developed film (heating step).

[0213] In the heating step, for example, when the photosensitive film contains a precursor such as a polyimide precursor or a polybenzoxazole precursor, or when the photosensitive film contains a crosslinking component such as a crosslinking agent, a cured pattern (also referred to as a "cured film") can be obtained.

[0214] It is preferred that a heating step be included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, crosslinking of unreacted crosslinking agent can be performed. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, further preferably 150°C or higher, further preferably 160°C or higher, and further preferably 170°C or higher. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, further preferably 350°C or lower, further preferably 250°C or lower, and further preferably 220°C or lower.

[0215] Regarding heating, it is preferred that the heating be performed at a heating rate of 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 the acid or solvent, and by setting the heating rate to 12°C / minute or less, it is possible to relax the residual stress of the pattern. In addition, in the case of an oven capable of rapid heating, it is preferred that the heating be performed at a heating rate of 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.

[0216] 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 heating process to the maximum heating temperature. For example, when a photosensitive resin composition is applied to a substrate and then dried, this refers to the temperature of the dried film (layer). For example, it is preferable 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.

[0217] The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

[0218] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, more preferably 180°C to 260°C. The reason for this is not yet clear, but it is believed that this temperature causes a cross-linking reaction between the acetylene groups of the specific resin between the layers.

[0219] Heating can be carried out in stages. As an example, a pretreatment process can be performed in which the temperature is raised from 25°C to 180°C at 3°C / min and maintained at 180°C for 60 minutes, and the temperature is raised from 180°C to 200°C at 2°C / min and maintained at 200°C for 120 minutes. The heating temperature as the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In this pretreatment process, as described in the specification of U.S. Patent No. 9159547, it is also preferred to treat while irradiating ultraviolet rays. The properties of the film can be improved by these pretreatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a step of two or more stages. For example, pretreatment process 1 can be carried out in the range of 100-150°C, and then pretreatment process 2 can be carried out in the range of 150-200°C.

[0220] Furthermore, the heating may be followed by cooling. In this case, the cooling rate is preferably 1 to 5° C. / min.

[0221] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[0222] The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, and a hot air oven.

[0223] <Metal layer formation process>

[0224] The pattern forming method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the pattern after the exposure steps such as the first region exposure step and the second region exposure step.

[0225] 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 even more preferred.

[0226] The formation method of the metal layer is not particularly limited, and existing methods can be applied. For example, the method described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be utilized. 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, or a patterning method combining photolithography and electrolytic plating can be cited.

[0227] The thickness of the metal layer is, for example, 0.01 to 100 μm at the thickest portion, preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

[0228] <Application>

[0229] Examples of fields in which the pattern obtained by the pattern forming method of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and cases where patterns are formed by etching insulating films for practical installation purposes, such as those described above. For information on these applications, reference can be made to, for example, "Higher Functionality and Application Technology of Polyimides" by Science & Technology Co., Ltd., April 2008, supervised by Masaaki Kakimoto, "Fundamentals and Development of Polyimide Materials" by CMC Technical Library, November 2011, and "Latest Polyimide Fundamentals and Applications" by the Japan Polyimide and Aromatic Polymer Research Society, NTS, August 2010.

[0230] Furthermore, the pattern obtained by the pattern forming method of the present invention can also be used in the production of offset printing plates, screen printing plates, and other plates, in the use of etched parts, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0231] (Method for producing laminate)

[0232] The method for producing a laminate of the present invention preferably includes the pattern forming method of the present invention.

[0233] The laminate obtained by the method for producing a laminate of the present invention is a laminate having a pattern of two or more layers, and may be a laminate having 3 to 7 layers stacked.

[0234] The pattern contained in the laminated body of the present invention may be the above-mentioned cured film.

[0235] Among the two or more patterns contained 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 pattern shape, all the patterns contained in the above-mentioned laminate are preferably patterns obtained by the pattern forming method of the present invention.

[0236] The laminate preferably includes two or more patterns and a metal layer between any of the patterns. The metal layer is preferably formed by the metal layer forming step.

[0237] As the laminate, for example, a laminate having a layer structure in which at least three layers, namely, a first pattern, a metal layer, and a second pattern, are sequentially laminated can be preferably mentioned.

[0238] Both the first pattern and the second pattern are preferably patterns obtained by the pattern forming method of the present invention. The photosensitive resin composition of the present invention used to form the first pattern and the photosensitive resin composition of the present invention used to form the second pattern may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

[0239] <Lamination process>

[0240] The method for producing a laminated body of the present invention preferably includes a lamination step.

[0241] The lamination process is a series of processes including sequentially performing (a) a film forming process (layer forming process), (b) a first region exposure process, (c) a second region exposure process, and (d) a development process on the surface of the pattern or metal layer.

[0242] However, the method may be such that only the steps (a) of film formation are repeated followed by the steps (b) of first area exposure and subsequent steps. Furthermore, after the step (c) of second area exposure, one or more steps of exposure such as a third area exposure step and a fourth area exposure step may be included.

[0243] Furthermore, the heating step may be included after the development step (d).

[0244] Furthermore, the metal layer forming step described above may be included after the (d) developing step. The lamination step may also include the drying step described above as appropriate.

[0245] When a further lamination step is performed after the lamination step, a surface activation step may be further performed after the exposure step, the development step, the heating step, or the metal layer formation step.

[0246] The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

[0247] For example, a structure in which the resin layer is set to more than 2 layers and less than 20 layers such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer can be cited, preferably a structure in which the resin layer is set to more than 3 layers and less than 7 layers, and more preferably a structure in which the resin layer is set to more than 3 layers and less than 5 layers.

[0248] Furthermore, the layers in the lamination step may be the same in composition, shape, thickness, etc., or may be different in composition, shape, thickness, etc.

[0249] Surface activation treatment process

[0250] The method for producing a cured film of the present invention may include a surface activation step of performing surface activation treatment on at least a portion of the metal layer and the photosensitive resin composition layer.

[0251] The surface activation treatment step is usually performed after the metal layer forming step. However, the metal layer forming step may be performed after the above-mentioned exposure and development steps and then after the photosensitive resin composition layer is subjected to the surface activation treatment step.

[0252] The surface activation treatment may be performed only on at least a portion of the metal layer, only on at least a portion of the exposed photosensitive resin composition layer, or on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. The surface activation treatment is preferably performed on at least a portion of the metal layer, and more preferably on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed. As described above, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion between the metal layer and the resin layer provided on the surface.

[0253] Furthermore, the surface activation treatment is preferably performed on a portion or the entirety of the exposed photosensitive resin composition layer (resin layer). As described above, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, adhesion to the metal layer or resin layer provided on the surface activated surface can be improved.

[0254] Specifically, the surface activation treatment can 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, immersion in aqueous hydrochloric acid solution to remove the oxide film and then immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, mechanical roughening treatment using a brush, preferably plasma treatment, and particularly preferably oxygen plasma treatment using oxygen as the raw material gas. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J / m 2 , more preferably 1,000 to 100,000 J / m 2 , most preferably 10,000 to 50,000 J / m 2 .

[0255] In the present invention, a method of forming a pattern of the photosensitive resin composition after providing a metal layer so as to cover the metal layer is particularly preferred. Specifically, a method of repeating the following sequence is used: (a) film formation step (layer formation step), (b) first area exposure step, (c) second area exposure step, (d) development step, and (e) metal layer formation step. By alternating the patterning steps (a) to (d) and the metal layer formation step, patterns and metal layers can be alternately laminated.

[0256] (Method for Manufacturing Electronic Device)

[0257] The present invention also discloses a method for manufacturing a semiconductor device including the pattern forming method of the present invention or the method for manufacturing a laminate of the present invention. Specific examples of semiconductor devices in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357, which are incorporated herein by reference.

[0258] Hereinafter, the photosensitive resin composition used in the pattern forming method of the present invention, the method for producing a laminated body of the present invention, or the method for producing a semiconductor device of the present invention will be described in detail.

[0259] (Photosensitive resin composition)

[0260] The photosensitive resin composition of the present invention is a photosensitive resin composition used in the pattern forming method of the present invention, the method for producing a laminated body of the present invention, or the method for producing a semiconductor device of the present invention.

[0261] The photosensitive resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor, and a photosensitizer.

[0262] Hereinafter, the details of each component contained in the photosensitive resin composition of the present invention will be described.

[0263] <Specified resin>

[0264] The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor.

[0265] The photosensitive resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

[0266] Furthermore, the specific resin preferably has a radical polymerizable group.

[0267] When the specific resin has a radical polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator as described below as a photosensitizer, more preferably contains a photoradical polymerization initiator as described below as a photosensitizer and a radical crosslinking agent as described below, and even more preferably contains a photoradical polymerization initiator as described below as a photosensitizer, a radical crosslinking agent as described below, and a sensitizer as described below. For example, a negative-type photosensitive layer is formed from such a photosensitive resin composition.

[0268] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0269] When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator as described below as a photosensitizer. For example, a chemically amplified positive-type photosensitive layer or a negative-type photosensitive layer is formed from such a photosensitive resin composition.

[0270] 〔Polyimide precursor〕

[0271] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).

[0272] Formula (2)

[0273] [Chemical Formula 1]

[0274]

[0275] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or NH, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group.

[0276] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or NH, and is preferably an oxygen atom.

[0277] R in formula (2) 111Represents a divalent organic group. As a divalent organic group, a group comprising a straight-chain or branched aliphatic group, a cyclic aliphatic group and an aromatic group can be exemplified, preferably a straight-chain 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, more preferably a group comprising an aromatic group having 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, the case of a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

[0278] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0279] Specifically, diamines 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 are preferred, and diamines containing a group consisting of an aromatic group having 6 to 20 carbon atoms are more preferred. Examples of the aromatic group include the following aromatic groups.

[0280] [Chemical Formula 2]

[0281]

[0282] In the formula, A is preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, NHCO- or a combination of these, more preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0283] In the formula, * represents the bonding site with other structures.

[0284] Specific examples of the diamine include 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; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenylenediamine; Benzene or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy- 4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 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'-diaminodiphenyl sulfone, 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-diamino Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2- hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, At least one diamine selected from the group consisting of 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaternaryl.

[0285] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0286] 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.

[0287] From the viewpoint of the flexibility of the obtained organic film, R 111Preferably, it is represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO2-, or NHCO-, or a group composed 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 that may be substituted with fluorine atoms, -O-, -CO-, -S-, or SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0288] From the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred.

[0289] Formula (51)

[0290] [Chemical Formula 3]

[0291]

[0292] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group.

[0293] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0294] [Chemical Formula 4-1]

[0295]

[0296] In formula (61), R 58 and R 59 are each independently a fluorine atom or a trifluoromethyl group.

[0297] Examples of the diamine compound that imparts 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 can be used alone or in combination of two or more.

[0298] Furthermore, the following diamines can also be preferably used.

[0299] [Chemical Formula 4-2]

[0300]

[0301] R in formula (2) 115 represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6). Formula (5)

[0302] [Chemical Formula 5]

[0303]

[0304] In formula (5), R 112 Preferably, it is 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-, -SO2- and NHCO-, and a group selected from a combination thereof; more preferably, it is a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and SO2-; further preferably, it is a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and SO2-.

[0305] Formula (6)

[0306] [Chemical Formula 6]

[0307]

[0308] Specifically, R 115 Examples thereof include a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0309] Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0310] Formula (O)

[0311] [Chemical Formula 7]

[0312]

[0313] In formula (O), R 115 Represents a tetravalent organic group. 115 The meaning of the preferred range is the same as that of R in formula (2) 115 The preferred ranges are also the same.

[0314] 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 tetracarboxylic dianhydride, anhydride, 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 alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms thereof.

[0315] Furthermore, as preferred examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned.

[0316] R is also preferred 111 and R 115 More specifically, at least one of R 111 , for example, residues of bisaminophenol derivatives.

[0317] R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, preferably R 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. As a polymerizable group, it is a group that can undergo a cross-linking reaction by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group can be enumerated. As the free radical polymerizable group possessed by a polyimide precursor, it is preferably a group with an ethylenically unsaturated bond.

[0318] Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). A group represented by the following formula (III) is preferred.

[0319] [Chemical Formula 8]

[0320]

[0321] In formula (III), R 200 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0322] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or a polyalkyleneoxy group.

[0323] Regarding the preferred R 201 Examples of include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. More preferred are ethylene, propylene, trimethylene, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. From the viewpoint of easily satisfying formula (2) in an organic film, further preferred are polyalkyleneoxy groups.

[0324] In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups of the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

[0325] When the polyalkyleneoxy group includes a plurality of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be random, block-wise, or alternating.

[0326] The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0327] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, and a halogen atom.

[0328] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0329] From the perspective of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups are bonded to multiple propyleneoxy groups. Polyethyleneoxy groups or polypropyleneoxy groups are more preferred, and polyethyleneoxy groups are even more preferred. In the group in which multiple ethyleneoxy groups are bonded to multiple propyleneoxy groups, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred embodiments of the number of repetitions of the ethyleneoxy group and the like in these groups are as described above.

[0330] R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include aromatic groups and aralkyl groups having an acid group bonded to one, two, or three (preferably one) carbon atoms constituting the aryl group. Specifically, examples include aromatic groups having 6 to 20 carbon atoms and having an acid group, and aralkyl groups having 7 to 25 carbon atoms and having an acid group. More specifically, examples include phenyl groups and benzyl groups having an acid group. The acid group is preferably an OH group.

[0331] R 113 or R 114 A hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group are also preferred.

[0332] From the perspective of solubility in organic solvents, R 113 or R 114 A monovalent organic group is preferred. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

[0333] The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic or polycyclic cyclic alkyl group. As the cyclic alkyl of monocycle, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl can be enumerated. As the cyclic alkyl of polycycle, for example, adamantyl, norbornyl, bornyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, dicyclohexyl and pinenyl (pinenyl) can be enumerated. Among them, from the viewpoint of taking into account high sensitivity, cyclohexyl is most preferably considered. And, as the alkyl substituted by aromatic groups, it is preferably a straight-chain alkyl substituted by aromatic groups described later.

[0334] Specific examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenene ring, a perylene ring, a pentacene ring, an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, Preferably, the ring is a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a benzopyran ring, a xanthene ring, a phenoxathiol ring, a phenothiazine ring or a phenazine ring. Most preferably, the ring is a benzene ring.

[0335] In formula (2), in R 113 In the case of a hydrogen atom or R 114 When it is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0336] R 113 and R 114At least one of the groups may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. Preferred groups include acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups. From the perspective of exposure sensitivity, acetal groups are more preferred.

[0337] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0338] Furthermore, the polyimide precursor also preferably has fluorine atoms in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0339] Furthermore, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0340] 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 width of the exposure latitude can be further expanded.

[0341] Formula (2-A)

[0342] [Chemical Formula 9]

[0343]

[0344] In formula (2-A), A 1 and A 2 represents oxygen atom, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, and preferably both of them are polymerizable groups.

[0345] A 1 、A 2 、R 111 、R 113 and R114 The meanings of are independently the same as those of A in formula (2) 1 、A 2 、R 111 、R 113 and R 114 The preferred ranges are also the same.

[0346] R 112 The meaning of is the same as R in formula (5) 112 The preferred ranges are also the same.

[0347] The polyimide precursor may contain one or more repeating structural units represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating structural units represented by formula (2). Furthermore, in addition to the repeating units of formula (2), the polyimide precursor may contain other types of repeating structural units.

[0348] One embodiment of the polyimide precursor of the present invention includes a polyimide precursor in which 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).

[0349] 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 even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0350] The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, even more preferably 3.8 or less, even more preferably 3.2 or less, even more preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.

[0351] In this specification, the molecular weight dispersion is a value calculated by dividing the weight average molecular weight by the number average molecular weight.

[0352] 〔Polyimide〕

[0353] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent.

[0354] In this specification, an alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C. From the perspective of pattern formation, the amount of polyimide that dissolves is preferably 0.5 g or more, and more preferably 1.0 g or more. The upper limit of the amount of polyimide that dissolves is not particularly limited, but is preferably 100 g or less.

[0355] Furthermore, from the viewpoint of film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0356] In this specification, a "main chain" refers to a relatively longest bond chain in the molecules of a polymer compound constituting a resin, and a "side chain" refers to other bond chains.

[0357] -Fluorine atom-

[0358] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms.

[0359] The fluorine atom is preferably contained in R in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by formula (4) described later 131 Among them, R is more preferably included as a fluorinated alkyl group in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by formula (4) described later 131 .

[0360] 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.

[0361] -Silicon atoms-

[0362] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has silicon atoms.

[0363] The silicon atom is preferably included in, for example, R in the repeating unit represented by the formula (4) described later. 131 More preferably, R is included in the repeating unit represented by the formula (4) described later as the organic modified (poly)siloxane structure described later. 131 .

[0364] Furthermore, the silicon atom or the organo-modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.

[0365] The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

[0366] -Ethylenically unsaturated bond-

[0367] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0368] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0369] The ethylenically unsaturated bond preferably has radical polymerizability.

[0370] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by formula (4) described later 131 More preferably, R is included in the repeating unit represented by the formula (4) described later as a group having an ethylenically unsaturated bond. 132 or R in the repeating unit represented by formula (4) described later 131 .

[0371] Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by formula (4) described later. 131 More preferably, R is included in the repeating unit represented by the formula (4) described later as a group having an ethylenically unsaturated bond. 131 .

[0372] Examples of the group having an ethylenically unsaturated bond include groups 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)acryloyloxy group, and a group represented by the following formula (IV).

[0373] [Chemical Formula 10]

[0374]

[0375] In formula (IV), R 20 represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0376] In formula (IV), R 21 It 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 number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these.

[0377] Among these, R 21It is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).

[0378] [Chemical Formula 11]

[0379]

[0380] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group 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 the bonding site with R in formula (III). 201 The bonding site of the bonded oxygen atom.

[0381] In formulae (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the same as that of the above R 21 The preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms is the same.

[0382] In formula (R1), X is preferably an oxygen atom.

[0383] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.

[0384] The structure represented by formula (R1) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).

[0385] 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 ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0386] The structure represented by formula (R3) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0387] In formula (IV), * represents a bonding site to another structure, preferably a bonding site to the main chain of the polyimide.

[0388] 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.

[0389] - Crosslinking groups other than ethylenically unsaturated bonds-

[0390] The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.

[0391] Examples of the crosslinkable group other than the ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

[0392] The crosslinking group other than the ethylenically unsaturated bond is preferably included in, for example, R in the repeating unit represented by the formula (4) described later. 131 .

[0393] The amount of the crosslinkable groups excluding 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.

[0394] -Polarity conversion group-

[0395] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and the R 113 and R 114 The acid-decomposable groups described in are the same and the preferred embodiments are also the same.

[0396] -Acid value-

[0397] When the polyimide is used for alkali development, 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, from the viewpoint of improving developability.

[0398] Furthermore, 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.

[0399] When the polyimide is used for development using a developer containing an organic solvent as the main component (for example, "solvent development" described below), 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.

[0400] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0401] Furthermore, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred, from the viewpoint of achieving both storage stability and developability.

[0402] pKa refers to the equilibrium constant, Ka, expressed as its negative common logarithm, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is assumed to be a value calculated using ACD / ChemSketch (registered trademark). Alternatively, reference can be made to the values ​​listed in "Chemical Handbook, 5th Revised Edition," edited by the Chemical Society of Japan.

[0403] Furthermore, when the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0404] As such an acid group, the polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0405] -Phenolic hydroxyl group-

[0406] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0407] The polyimide may have a phenolic hydroxyl group at a main chain terminal or a side chain.

[0408] The phenolic hydroxyl group is preferably included in R in the repeating unit represented by the formula (4) described later. 132 or R in the repeating unit represented by formula (4) described later 131 .

[0409] 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.

[0410] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and more preferably contains a repeating unit represented by formula (4) and has a polymerizable group.

[0411] Formula (4)

[0412] [Chemical Formula 12]

[0413]

[0414] In formula (4), R 131 Represents a divalent organic group, R 132 represents a tetravalent organic group.

[0415] When there is a polymerizable group, the polymerizable group can be located at R 131 and R 132 At least one of them may be located at a terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0416] Formula (4-1)

[0417] [Chemical Formula 13]

[0418]

[0419] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0420] Formula (4-2)

[0421] [Chemical Formula 14]

[0422]

[0423] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

[0424] The polymerizable group has the same meaning as that described for the polymerizable group possessed by the aforementioned polyimide precursor and the like.

[0425] R 131 Represents a divalent organic group. Examples of the divalent organic group include the following: 111 The same organic group has the same preferred range.

[0426] And, as R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 example.

[0427] From the perspective of more effectively suppressing warpage during firing, R 131 A diamine residue having at least two alkylene glycol units in the main chain is preferred, a diamine residue containing two or more ethylene glycol chains or propylene glycol chains or both in one molecule is more preferred, and a diamine residue containing no aromatic ring is even more preferred.

[0428] Examples of the diamine containing a total of two or more ethylene glycol chains or propylene glycol chains, or both, 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.

[0429] R 132 Represents a tetravalent organic group. Examples of the tetravalent organic group include the following: 115 The same organic group has the same preferred range.

[0430] For example, as R 115 The four connecting bonds of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring.

[0431] [Chemical Formula 15]

[0432]

[0433] And, R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0434] Also preferably in R 131 and R 132 More specifically, as R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)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 mentioned as preferred examples, and as R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be mentioned.

[0435] Furthermore, the polyimide also preferably has fluorine atoms in its structural units. The content of fluorine atoms in the polyimide is preferably 10% by mass or more and preferably 20% by mass or less.

[0436] Furthermore, in order to improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0437] Furthermore, in order to improve the storage stability of the composition, the main chain ends of the polyimide are preferably sealed with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds. Among these, monoamines are more preferably used. Preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 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 end-capping agents.

[0438] -Imidization rate (ring closure rate)-

[0439] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

[0440] The upper limit of the imidization rate is not particularly limited, but may be 100% or less.

[0441] The imidization ratio can be measured, for example, by the following method.

[0442] The infrared absorption spectrum of polyimide was measured and the absorption peak at 1377 cm-1 derived from the imide structure was found. -1 Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0443] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0444] The polyimide may include one R 131 or R 132 The repeating structural unit of the above formula (4) may also include two or more different types of R 131 or R 132 The polyimide may contain other types of repeating structural units in addition to the repeating units of the formula (4).

[0445] Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with a diamine compound (partially substituted with a monoamine, i.e., a capping agent) at low temperature; reacting tetracarboxylic dianhydride (partially 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; obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the resulting mixture in the presence of a diamine (partially substituted with a monoamine, i.e., a capping agent) and a condensing agent; obtaining a diester from tetracarboxylic dianhydride and an alcohol and then chlorinating the remaining dicarboxylic acid and reacting the resulting mixture with a diamine (partially substituted with a monoamine, i.e., a capping agent); and obtaining a polyimide precursor by a known imidization reaction method to achieve complete imidization, or by terminating the imidization reaction midway and introducing a partial imide structure; or further, by mixing a completely imidized polymer and its polyimide precursor to introduce a partial imide structure.

[0446] Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation).

[0447] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Furthermore, when containing two or more polyimides, the weight average molecular weight of at least one polyimide is preferably within the above range.

[0448] [Polybenzoxazole precursor]

[0449] The polybenzoxazole precursor used in the present invention is not particularly limited in its structure, but preferably contains a repeating unit represented by the following formula (3).

[0450] Formula (3)

[0451] [Chemical Formula 16]

[0452]

[0453] In formula (3), R 121 Represents a divalent organic group, R 122 Represents a 4-valent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0454] In formula (3), R 123 and R 124 The meanings of are respectively the same as R in formula (2) 113 That is, at least one is preferably a polymerizable group.

[0455] In formula (3), R 121 Represents a divalent organic group. As a divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As an aliphatic group, a straight-chain aliphatic group is preferred. R 121 A dicarboxylic acid residue is preferably used. Only one dicarboxylic acid residue may be used, or two or more dicarboxylic acid residues may be used.

[0456] The dicarboxylic acid residue is preferably a dicarboxylic acid residue containing an aliphatic group or a dicarboxylic acid residue containing an aromatic group, and more preferably a dicarboxylic acid residue containing an aromatic group.

[0457] The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10 carbon atoms. The linear aliphatic group is preferably an alkylene group.

[0458] Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylheptanedioic acid, and 1,2,6,6-tetramethylheptanedioic 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 , behenedioic acid, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diethylene glycol acid, and dicarboxylic acid represented by the following formula.

[0459] [Chemical Formula 17]

[0460]

[0461] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0462] 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.

[0463] [Chemical Formula 18]

[0464]

[0465] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * each independently represents a bonding site with other structures.

[0466] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4′-carbonyldibenzoic acid, 4,4′-dicarboxydiphenyl ether, and terephthalic acid.

[0467] In formula (3), R 122 Represents a quaternary organic group. As a quaternary organic group, the meaning is the same as R in the above formula (2) 115 The preferred ranges are also the same.

[0468] And, R 122Preferred are groups derived from bisaminophenol derivatives. Examples of the groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-( 4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

[0469] Among the bisaminophenol derivatives, those having the following aromatic groups are preferred.

[0470] [Chemical Formula 19]

[0471]

[0472] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, * and # represent the bonding sites with other structures. 122 The structure represented by the above formula is also preferred. 122 In the case of the structure represented by the above formula, it is preferred that any two of the four * and # are the same as R in formula (3). 122 The bonding site of the nitrogen atom to which the bond is attached and the other two are R in formula (3) 122 The bonding site of the oxygen atom to which the bond is bonded is more preferably 2*, which is the same as R in formula (3). 122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded or the two * are R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded and the two # are the same as R in formula (3) 122 The bonding site of the oxygen atom to which the bond is bonded is preferably 2*, which is the same as R in formula (3). 122 The bonding site of the bonded oxygen atom and the two # are the same as R in formula (3) 122The bonding site of the bonded nitrogen atom.

[0473] [Chemical Formula 20]

[0474]

[0475] 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 represented by formula (A-sc) below. 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.

[0476] [Chemical Formula 21]

[0477]

[0478] (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

[0479] In the above formula (As), it is believed that having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, brings the carbonyl carbon of the amide bond and the hydroxyl group closer together, and is particularly preferred from the perspective of further improving the effect of high cyclization rate during curing at low temperatures.

[0480] Furthermore, in the above formula (As), when R2 and R3 are both alkyl groups, high transparency to i-rays can be maintained and the cyclization rate can be increased during curing at low temperatures, which is preferred.

[0481] Furthermore, in the above formula (As), R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group associated with 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)(CH2CH2CH2CH3)-, -CH(CH2CH(CH3) )2)-, -C(CH3)(CH2CH(CH3)2)-, -CH(CH2CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH2CH3)-, -CH(CH2CH2CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH2CH3)-, -CH(CH2CH2CH2CH2CH2CH3)-, -C(CH3)(CH2CH2CH2CH2CH2CH3)-, etc. Among them, from the viewpoint of being able to obtain a polybenzoxazole precursor having an excellent balance of maintaining high transparency to i-rays and an effect of increasing the cyclization rate during curing at low temperatures while having sufficient solubility in solvents, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred.

[0482] As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506, the contents of which are incorporated herein.

[0483] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated herein, but are not limited thereto.

[0484] In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating structural units.

[0485] From the viewpoint of being able to suppress warpage caused by ring closure, it is preferred to contain a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

[0486] [Chemical Formula 22]

[0487]

[0488] In formula (SL), Z has structures a and b, and R 1sis a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s 、R 4s 、R 5s 、R 6s At least one of the groups is an aromatic group, and the remaining groups are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structures a and b may be block or random. Regarding the mole % of the Z portion, structure a is 5 to 95 mole %, structure b is 95 to 5 mole %, and a + b is 100 mole %.

[0489] In formula (SL), preferred Z includes R in structure b. 5s and R 6s Z is a phenyl group. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

[0490] When a diamine residue represented by 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 tetracarboxylic acid residues include R in formula (2): 115 example.

[0491] For example, when used in the composition described below, the polybenzoxazole precursor preferably has a weight average molecular weight (Mw) of 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0492] The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or greater, more preferably 1.5 or greater, and even more preferably 1.6 or greater. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0493] Polybenzoxazole

[0494] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a free radical polymerizable group. Furthermore, the compound may be represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.

[0495] [Chemical Formula 23]

[0496]

[0497] In formula (X), R 133 Represents a divalent organic group, R 134 represents a tetravalent organic group.

[0498] When a polarity conversion group such as a polymerizable group or an acid-decomposable group is present, the polymerizable group or the acid-decomposable group may be located at R 133 and R 134 At least one of them may be located at the terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

[0499] Formula (X-1)

[0500] [Chemical Formula 24]

[0501]

[0502] In formula (X-1), R 135 and R 136 At least one of them is a polymerizable group or a polarity converting group such as an acid-decomposable group, and when it is not a polymerizable group or a polarity converting group such as an acid-decomposable group, it is an organic group, and the other groups have the same meanings as in formula (X).

[0503] Formula (X-2)

[0504] [Chemical Formula 25]

[0505]

[0506] 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 other groups are the same as those in formula (X).

[0507] The meaning of the polarity conversion group such as the polymerizable group or the acid-decomposable group is the same as that of the polymerizable group described above with respect to the polymerizable group possessed by the polyimide precursor and the like.

[0508] R 133represents a divalent organic group. Examples of the divalent organic group include aliphatic groups and aromatic groups. As a specific example, R in the formula (3) of the polybenzoxazole precursor may be 121 And, the meaning of its preferred example is the same as R 121 same.

[0509] R 134 The tetravalent organic group includes R in the formula (3) of the polybenzoxazole precursor. 122 And, the meaning of its preferred example is the same as R 122 same.

[0510] For example, as R 122 The four connecting bonds of the exemplified tetravalent organic group are bonded to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. 134 When it is the following organic group, the following structure is formed.

[0511] [Chemical Formula 26]

[0512]

[0513] The oxazolidation rate of polybenzoxazole is preferably 85% or higher, more preferably 90% or higher. When the oxazolidation rate is 85% or higher, film shrinkage due to ring closure (occurring during oxazolidation by heating) is reduced, and warping can be effectively suppressed.

[0514] Polybenzoxazoles may include all of which contain one R 131 or R 132 The repeating structural unit of the above formula (X) may also include 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 contain other types of repeating structural units.

[0515] For example, a bisaminophenol derivative is reacted with a 133 A polybenzoxazole precursor is obtained by reacting a dicarboxylic acid or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids, and then oxazolidinone is formed by a known oxazolidinone reaction method to obtain polybenzoxazole.

[0516] In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative prepared by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to improve the reaction yield.

[0517] 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, the weight average molecular weight is particularly preferably 20,000 or more. Furthermore, 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.

[0518] [Method for producing polyimide precursor, etc.]

[0519] The polyimide precursor can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine, preferably by halogenating the dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the halogenated dicarboxylic acid with diamine.

[0520] 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 kind or two or more kinds.

[0521] The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

[0522] Polyimide can be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, by promoting the cyclization reaction by the action of a catalyst). Alternatively, polyimide can be directly synthesized.

[0523] -Capping agent-

[0524] When producing a polyimide precursor, etc., in order to further improve storage stability, it is preferred to seal the ends of the polyimide precursor, etc. with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or a monoactive ester compound. As the end-capping agent, a monoamine is 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, 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 end-capping agents.

[0525] -Solid precipitation-

[0526] When producing a polyimide precursor, etc., a solid precipitation step may be included. Specifically, the solid can be precipitated by precipitating the polyimide precursor, etc. in the reaction solution in water and then dissolving the polyimide precursor, etc., in a solvent such as tetrahydrofuran, in which the polyimide precursor, etc. is soluble.

[0527] Thereafter, by drying the polyimide precursor, etc., a powdery polyimide precursor, etc. can be obtained.

[0528] 〔content〕

[0529] The content of the resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total solids content of the composition. Furthermore, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the composition.

[0530] The composition of the present invention may contain only one resin or two or more resins. When containing two or more resins, the total amount is preferably within the above range.

[0531] <Other resins>

[0532] The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0533] Examples of other resins include polyamideimide, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.

[0534] For example, by further adding an acrylic resin, a composition having excellent coating properties can be obtained, and an organic film having excellent solvent resistance can be obtained.

[0535] For example, by adding an acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group valence 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.

[0536] 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, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the composition.

[0537] Furthermore, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the composition.

[0538] Furthermore, as a preferred embodiment of the composition of the present invention, the composition can also be configured with a low content of other resins. In this embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, relative to the total solids content of the composition. The lower limit of this content is not particularly limited, and 0% by mass or more is sufficient.

[0539] The composition of the present invention may contain only one other resin or two or more other resins. When containing two or more other resins, the total amount is preferably within the above range.

[0540] <Photosensitive agent>

[0541] The composition of the present invention comprises a photosensitizer.

[0542] As the photosensitizer, a photopolymerization initiator is preferred.

[0543] 〔Photopolymerization initiator〕

[0544] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.

[0545] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations 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 to visible regions is preferred. Furthermore, an activator that reacts with a photoexcited sensitizer to generate active free radicals may be used.

[0546] In the organic film, from the viewpoint of easily satisfying the above formula (2), the composition of the present invention preferably contains the metal element-containing compound described below as a photoradical polymerization initiator. That is, in the present invention, among the metal element-containing compounds described below, a metal element-containing compound having a radical polymerization initiation ability can be used as the photoradical polymerization initiator.

[0547] Here, "having the ability to initiate free radical polymerization" means being able to generate free radicals capable of initiating free radical polymerization. For example, when a composition comprising a free radical polymerizable monomer, a binder polymer, and a metal element-containing compound is irradiated with light in a wavelength range where the metal element-containing compound absorbs light but the free radical polymerizable monomer does not, the presence or absence of polymerization initiation ability can be confirmed by confirming whether the free radical polymerizable monomer disappears. Confirming whether this disappearance occurs can be done by selecting an appropriate method depending on the type of free radical polymerizable monomer and binder polymer, such as IR (infrared spectroscopy) or HPLC (high performance liquid chromatography).

[0548] When the composition of the present invention contains a metal element-containing compound having the ability to initiate free radical polymerization, the composition of the present invention preferably also contains substantially no free radical polymerization initiators other than the metal element-containing compound. Substantially containing no free radical polymerization initiators other than the metal element-containing compound means that the content of free radical polymerization initiators other than the metal element-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, relative to the total mass of the metal element-containing compound.

[0549] Furthermore, when the composition of the present invention contains a metal element-containing compound having radical polymerization initiation ability, the composition of the present invention also preferably contains the metal element-containing compound and another photoradical polymerization initiator.

[0550] When the composition of the present invention contains a metal element-containing compound and other photoradical polymerization initiators, the content of the metal element-containing compound relative to the total content of the metal element-containing compound and other photoradical polymerization initiators is preferably 20 to 80 mass %, more preferably 30 to 70 mass %.

[0551] Furthermore, as the other photoradical polymerization initiator, an oxime compound described below is preferable.

[0552] The photoradical polymerization initiator preferably contains at least one having a wavelength of at least about 50 L / mol in the range of about 300 to 800 nm (preferably 330 to 500 nm). -1 / cm -1 The molar absorptivity of a compound can be measured using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate as a solvent at a concentration of 0.01 g / L.

[0553] As a photoradical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azides, metallocene compounds, organic boron compounds, iron arene complexes, etc. can be cited. For details of these, 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, which are incorporated herein by reference.

[0554] Examples of ketone compounds 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.

[0555] 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 Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

[0556] 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.

[0557] As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0558] As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, which have an absorption maximum wavelength that matches a light source having a wavelength of 365 nm or 405 nm, can also be used.

[0559] Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can also be used.

[0560] 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 radical polymerization initiation ability) described below.

[0561] As the photoradical polymerization initiator, oxime compounds are more preferably used. By using oxime compounds, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as photocuring accelerators, so they are particularly preferred.

[0562] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.

[0563] Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-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 an oxime compound as a photoradical polymerization initiator (oxime-based photopolymerization initiator). Oxime-based photopolymerization initiators have a linking group >C=NOC(=O)- in the molecule.

[0564] [Chemical Formula 27-1]

[0565]

[0566] Among the commercially available 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, a photoradical polymerization initiator 2 described in JP-A-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 DAITOCHEMIX Co., Ltd.) can be used. In addition, oxime compounds of the following structures can also be used.

[0567] [Chemical Formula 27-2]

[0568]

[0569] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081.

[0570] As the photopolymerization initiator, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013 / 083505.

[0571] 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.

[0572] The most preferred oxime compounds include oxime compounds having a specific substituent as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061.

[0573] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine 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, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0574] More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds, and it is further preferred to use oxime compounds.

[0575] Furthermore, photoradical polymerization initiators that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones formed by condensing an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoins, and benzyl derivatives such as benzyl dimethyl ketal. Furthermore, compounds represented by the following formula (I) can also be used.

[0576] [Chemical Formula 28]

[0577]

[0578] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, 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 or a biphenyl group substituted with 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, R I01 is a group represented by formula (II), or is I00 The same group, R I02 ~R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen group.

[0579] [Chemical Formula 29]

[0580]

[0581] Where R I05 ~R I07 and R of the above formula (I) I02 ~R I04 same.

[0582] Furthermore, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used.

[0583] When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass relative to the total solid content of the composition of the present invention. A single photopolymerization initiator may be included, or two or more may be included. When two or more photopolymerization initiators are included, the total amount is preferably within the above range.

[0584] 〔Photoacid generator〕

[0585] Furthermore, the composition of the present invention also preferably contains a photoacid generator as a photosensitizer.

[0586] By including a photoacid generator, for example, acid is generated in the exposed portion of the composition layer, thereby increasing the solubility of the exposed portion in a developer (eg, an alkaline aqueous solution), and a positive pattern can be obtained in which the exposed portion is removed by the developer.

[0587] Furthermore, by containing a photoacid generator and a polymerizable compound other than the radical polymerizable compound described below, for example, the crosslinking reaction of the polymerizable compound can be accelerated by the acid generated in the exposed areas, making the exposed areas less susceptible to removal by the developer than the non-exposed areas. This allows for the production of a negative-tone pattern.

[0588] The photoacid generator is not particularly limited as long as it generates acid upon exposure, and examples thereof include quinonediazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imide sulfonates, oxime sulfonates, diazonium disulfones, disulfones, and o-nitrobenzyl sulfonate.

[0589] Examples of the quinonediazide compound include compounds in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester, compounds in which the sulfonic acid of quinonediazide is bonded to a polyamino compound via a sulfonamide bond, and compounds in which the sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferred that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

[0590] In the present invention, as quinone diazide, 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group can be preferably used. 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-ray region of mercury lamp, and is therefore suitable for i-ray exposure. 5-naphthoquinone diazide sulfonyl ester compound has absorption extending to the g-ray region of mercury lamp, and is therefore suitable for g-ray exposure. In the present invention, 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound are preferably selected according to the wavelength for exposure. In addition, naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, and 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound may also be contained.

[0591] The naphthoquinonediazide compounds can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity, and residual film rate are further improved.

[0592] Examples of the naphthoquinonediazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds.

[0593] Examples of the onium salt compound or the sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

[0594] Commercially available photoacid generators may be used, and examples of commercially available photoacid generators 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).

[0595] When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 2 to 15% by mass relative to the total solids content of the composition of the present invention. A single photoacid generator may be included, or two or more may be included. When two or more photoacid generators are included, their total content is preferably within the above range.

[0596] Solvents

[0597] The photosensitive resin composition of the present invention preferably contains a solvent.

[0598] Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0599] 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), Preferred esters include alkyl 2-alkoxypropionates (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), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0600] Preferred ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosol acetate, ethyl cellosol 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, and propylene glycol monopropyl ether acetate.

[0601] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, and dihydrolevoglucosanone.

[0602] Preferred examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

[0603] As the sulfoxides, for example, dimethyl sulfoxide is mentioned as a preferable sulfoxide.

[0604] Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0605] Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0606] Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0607] From the viewpoint of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[0608] In the present invention, a solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-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 these is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Furthermore, combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone are also preferred.

[0609] The solvent content is preferably such that the total solids concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass, from the viewpoint of coating properties. The solvent content can be adjusted depending on the desired thickness of the coating film and the coating method.

[0610] The solvent may be contained alone or in combination of two or more. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0611] Thermal polymerization initiator

[0612] The composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals using thermal energy, thereby initiating or accelerating the polymerization reaction of a polymerizable compound. The addition of a thermal free radical polymerization initiator allows the polymerization reaction of the resin and the polymerizable compound to proceed even during the heating step described below, thereby further improving solvent resistance.

[0613] Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

[0614] When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 5 to 15% by mass relative to the total solid content of the composition of the present invention. The thermal polymerization initiator may be contained alone or in combination. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0615] Thermal acid generators

[0616] The compositions of the present invention may contain a thermal acid generator.

[0617] The thermal acid generator has the effect of generating an acid by heating, thereby promoting the crosslinking reaction of at least one compound selected from the group consisting of compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

[0618] The thermal decomposition starting temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. Furthermore, it is preferred to select a thermal acid generator that does not generate acid during drying (pre-baking: approximately 70°C to 140°C) after the composition is applied to a substrate, but generates acid during final heating (curing: approximately 100°C to 400°C) after pattern formation by subsequent exposure and development, because this can suppress a decrease in sensitivity during development.

[0619] 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 exothermic peak is determined as the thermal decomposition starting temperature.

[0620] Examples of the instrument used to measure the thermal decomposition onset temperature include Q2000 (manufactured by TA Instruments).

[0621] The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, or butanesulfonic acid, or a halogenated alkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

[0622] Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, the thermal acid generator is more preferably a substance that generates an alkylsulfonic acid having 1 to 4 carbon atoms or a halogenated alkylsulfonic acid having 1 to 4 carbon atoms, and preferably (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, trifluoromethane (4-Hydroxyphenyl)dimethylsulfonium sulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0623] Furthermore, the compound described in 0059 of JP-A-2013-167742 is also preferably used as the thermal acid generator.

[0624] The content of the thermal acid generator is preferably 0.01 parts by mass or greater, more preferably 0.1 parts by mass or greater, per 100 parts by mass of the resin. The inclusion of 0.01 parts by mass or greater promotes the crosslinking reaction, thereby further improving the mechanical properties and solvent resistance of the organic film. Furthermore, from the perspective of the electrical insulation properties of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0625] Onium salts

[0626] The composition of the present invention preferably comprises an onium salt.

[0627] In particular, when a polyimide precursor is contained as another resin, the composition preferably contains an onium salt.

[0628] The type of onium salt is not particularly limited, but preferred examples include ammonium salts, imide salts, sulfonium salts, iodonium salts, and phosphonium salts.

[0629] Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

[0630] Furthermore, an onium salt is a salt of a cation having an onium structure and an anion, and the cation and anion may or may not be bonded via a covalent bond.

[0631] That is, the onium salt may be an intramolecular salt having a cationic portion and an anionic portion within the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule of different molecules are ionically bonded, preferably an intermolecular salt. Furthermore, in the composition of the present invention, the cationic portion or cationic molecule and the anionic portion or anionic molecule may be ionically bonded or dissociated.

[0632] The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

[0633] The onium salt used in the present invention may also be a thermal base generator.

[0634] The thermal base generator refers to a compound that generates a base when heated, and examples thereof include acidic compounds that generate a base when heated to 40° C. or higher.

[0635] [Ammonium salt]

[0636] In the present invention, ammonium salt means a salt of an ammonium cation and an anion.

[0637] -Ammonium cation-

[0638] As the ammonium cation, a quaternary ammonium cation is preferred.

[0639] Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferable.

[0640] [Chemical formula 30]

[0641]

[0642] In formula (101), R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group, R 1 ~R 4 At least two of them may be bonded to form a ring.

[0643] In formula (101), R 1 ~R 4Each of them is independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. 1 ~R 4 It 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.

[0644] R 1 ~R 4 When at least two of the above are bonded to form a ring, the ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom.

[0645] The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2).

[0646] [Chemical Formula 31]

[0647]

[0648] In formulas (Y1-1) and (Y1-2), R 101 represents an n-valent organic group, R 1 The meaning of is the same as R in formula (101) 1 Same, Ar 101 and Ar 102 Each independently represents an aryl group, and n represents an integer of 1 or greater.

[0649] In formula (Y1-1), R 101 Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, or groups obtained by removing n hydrogen atoms from the structure to which these are bonded, and more preferred are saturated aliphatic hydrocarbons having 2 to 30 carbon atoms, or groups obtained by removing n hydrogen atoms from benzene or naphthalene.

[0650] In formula (Y1-1), n ​​is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0651] In formula (Y1-2), Ar 101 and Ar 102 Each independently is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

[0652] -Anions-

[0653] The anion in the ammonium salt is preferably one selected from the group consisting of a carboxylate anion, a phenolate anion, a phosphate anion, and a sulfate anion. A carboxylate anion is more preferred for the sake of achieving a balance between salt stability and thermal decomposition. Specifically, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.

[0654] The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. This embodiment can further improve the stability, curability, and developability of the composition. In particular, the use of an anion of a divalent carboxylic acid can further improve the stability, curability, and developability of the composition.

[0655] The carboxylate anion is preferably represented by the following formula (X1).

[0656] [Chemical Formula 32]

[0657]

[0658] In formula (X1), EWG represents an electron withdrawing group.

[0659] In this embodiment, the electron-withdrawing group indicates that the Hammett substituent constant σm is positive. σm is described in detail in "Tsuno Yufu's General Commentary, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), pp. 631-642." Furthermore, the electron-withdrawing group in this embodiment is not limited to the substituents described in the aforementioned literature.

[0660] Examples of substituents having a positive σm include a CF3 group (σm = 0.43), a CF3C(=O) group (σm = 0.63), an 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 an H2NC(=O)CH2 group (σm = 0.06). Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same shall apply hereinafter).

[0661] EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).

[0662] [Chemical Formula 33]

[0663]

[0664] In formulas (EWG-1) to (EWG-6), R x1 ~R x3 Each independently represents 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.

[0665] In the present invention, the carboxylate anion is preferably represented by the following formula (XA).

[0666] [Chemical Formula 34]

[0667]

[0668] In formula (XA), L 10 represents a single bond or is selected from alkylene, alkenylene, aromatic group, -NR X - and the divalent linking group in the combination thereof, R X represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

[0669] Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion.

[0670] From the viewpoint that the cyclization of the specific resin is easily carried out at low temperatures and the storage stability of the composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation and the above-mentioned onium salt preferably contains an anion having a pKa (pKaH) of a conjugate acid of 2.5 or less as an anion, more preferably containing an anion of 1.8 or less.

[0671] The lower limit of the pKa is not particularly limited, but is preferably -3 or higher, more preferably -2 or higher, from the viewpoint of preventing the generated base from being easily neutralized and improving the cyclization efficiency of a specific resin or the like.

[0672] The pKa values ​​described in Determination of Organic Structures by Physical Methods (Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Dawson, RMC et al; Oxford, Clarendon Press, 1959) can be used as reference. For compounds not described in these documents, values ​​calculated from the structural formula using ACD / pKa software (manufactured by ACD / Labs) were used.

[0673] Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[0674] [Chemical Formula 35]

[0675]

[0676] 〔Iminium salt〕

[0677] In the present invention, the iminium salt refers to a salt of an iminium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

[0678] -Iminium cation-

[0679] As the iminium cation, a pyridinium cation is preferred.

[0680] Furthermore, as the iminium cation, a cation represented by the following formula (102) is also preferred.

[0681] [Chemical Formula 36]

[0682]

[0683] In formula (102), R 5 and R 6 Each independently represents a hydrogen atom or a hydrocarbon group, R 7 Represents a hydrocarbon group, R 5 ~R 7 At least two of them may be bonded to form a ring.

[0684] In formula (102), R 5 and R 6 The meaning of is the same as R in the above formula (101) 1 ~R 4 Same, preferred method is also the same.

[0685] In formula (102), R 7 Optimum with R 5 and R 6 At least one of the above is bonded to form a ring. The above ring may contain a heteroatom. Examples of the above heteroatom include a nitrogen atom. Furthermore, the above ring is preferably a pyridine ring.

[0686] The iminium cation is preferably a cation represented by any one of the following formulae (Y1-3) to (Y1-5).

[0687] [Chemical Formula 37]

[0688]

[0689] In formulas (Y1-3) to (Y1-5), R 101 represents an n-valent organic group, R 5 The meaning of is the same as R in formula (102) 5 Same, R 7 The meaning of is the same as R in formula (102) 7 Similarly, n represents an integer greater than or equal to 1, and m represents an integer greater than or equal to 0.

[0690] In formula (Y1-3), R 101 Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, or groups obtained by removing n hydrogen atoms from the structure to which these are bonded, and more preferred are saturated aliphatic hydrocarbons having 2 to 30 carbon atoms, or groups obtained by removing n hydrogen atoms from benzene or naphthalene.

[0691] In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0692] In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

[0693] Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.

[0694] [Chemical Formula 38]

[0695]

[0696] Sulfonium salt

[0697] In the present invention, the sulfonium salt refers to a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

[0698] -Sulfonium cation-

[0699] The sulfonium cation is preferably a tertiary sulfonium cation, and more preferably a triarylsulfonium cation.

[0700] Furthermore, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

[0701] [Chemical Formula 39]

[0702]

[0703] In formula (103), R 8 ~R 10 Each independently represents a hydrocarbon group.

[0704] R 8 ~R 10 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0705] R 8 ~R 10The substituent may be substituted. 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, the substituent preferably has an alkyl group or an alkoxy group, more preferably has a branched alkyl group or an alkoxy group, and even more preferably has a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0706] R 8 ~R 10 They may be the same group or different groups, but are preferably the same group from the viewpoint of synthetic suitability.

[0707] Iodized salt

[0708] In the present invention, the 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.

[0709] -Iodine cation-

[0710] As the iodine cation, a diaryliodonium cation is preferred.

[0711] Furthermore, as the iodine cation, a cation represented by the following formula (104) is preferable.

[0712] [Chemical Formula 40]

[0713]

[0714] In formula (104), R 11 and R 12 Each independently represents a hydrocarbon group.

[0715] R 11 and R 12 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0716] R 11 and R 12 The substituent may be substituted. 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 substituents, 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 even more preferred.

[0717] R 11 and R 12They may be the same group or different groups, but are preferably the same group from the viewpoint of synthetic suitability.

[0718] Phosphonium salts

[0719] In the present invention, the phosphonium salt refers to a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

[0720] -Phosphonium cation-

[0721] The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.

[0722] Furthermore, the phosphonium cation is preferably a cation represented by the following formula (105).

[0723] [Chemical Formula 41]

[0724]

[0725] In formula (105), R 13 ~R 16 Each independently represents a hydrogen atom or a hydrocarbon group.

[0726] R 13 ~R 16 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0727] R 13 ~R 16 The substituent may be substituted. 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 substituents, 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 even more preferred.

[0728] R 13 ~R 16 They may be the same group or different groups, but are preferably the same group from the viewpoint of synthetic suitability.

[0729] When the composition of the present invention includes an onium salt, the content of the onium salt 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, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, and even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.

[0730] The onium salts may be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

[0731] Thermal alkali generator

[0732] The compositions of the present invention may contain a thermal base generator.

[0733] In particular, when the composition contains a polyimide precursor as another resin, the composition preferably contains a thermal base generator.

[0734] The thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be another thermal base generator other than the above-mentioned onium salt.

[0735] As other thermal base generating agents, nonionic thermal base generating agents can be mentioned.

[0736] Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

[0737] [Chemical Formula 42]

[0738]

[0739] 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 without a tertiary amine structure. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 None of them have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. 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 the nitrogen atom, the present invention is not limited thereto.

[0740] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3Preferably, at least one of these contains a cyclic structure, and more preferably at least two contain a cyclic structure. The cyclic structure can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensing two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0741] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12 carbon atoms). These groups may have a substituent within the scope of exerting the effect of the present invention. Rb 1 With Rb 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. In particular, Rb 1 and Rb 2 Preferably, it is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), and even more preferably a cyclohexyl group which may have a substituent.

[0742] As Rb 3 , examples include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12 carbon atoms), aralkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and further preferably 8 to 16 carbon atoms), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12 carbon atoms), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12 carbon atoms), and aralkyloxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), arylalkenyl, and arylalkyloxy groups are preferred. 3 It may further have a substituent within a range in which the effects of the present invention are exhibited.

[0743] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0744] [Chemical Formula 43]

[0745]

[0746] Where Rb 11 and Rb 12 and Rb 31 and Rb 32 The meanings of are respectively the same as Rb in formula (B1) 1 and Rb 2 same.

[0747] Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms), and may have a substituent within the range in which the effects of the present invention are exerted. 13 An aralkyl group is preferred.

[0748] Rb 33 and Rb 34 Each of them is independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and is preferably a hydrogen atom.

[0749] Rb 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and is preferably an aryl group.

[0750] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[0751] [Chemical Formula 44]

[0752]

[0753] Rb 11 and Rb 12 The meaning is the same as Rb in formula (B1-1) 11 and Rb 12 same.

[0754] Rb 15 and Rb 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom or a methyl group.

[0755] Rb 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0756] The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0757] Among the above-mentioned onium salts, specific examples of the compound serving as a thermal base generator and specific examples of other thermal base generators include the following compounds.

[0758] [Chemical Formula 45]

[0759]

[0760] [Chemical Formula 46]

[0761]

[0762] [Chemical Formula 47]

[0763]

[0764] The content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solids content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or greater, and even more preferably 1% by mass or greater. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or more thermal base generators may be used. When two or more thermal base generators are used, the total amount is preferably within the above range.

[0765] Cross-linking agent

[0766] The photosensitive resin composition of the present invention preferably contains a crosslinking agent.

[0767] Examples of the crosslinking agent include radical crosslinking agents and other crosslinking agents.

[0768] <Free Radical Crosslinking Agent>

[0769] The photosensitive resin composition of the present invention preferably further contains a radical crosslinking agent.

[0770] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferably used. As the group containing the above-mentioned ethylenically unsaturated bond, groups having an ethylenically unsaturated bond such as vinyl, allyl, vinylphenyl, and (meth)acryloyl can be mentioned.

[0771] Among these, as the group containing the above-mentioned ethylenically unsaturated bond, a (meth)acryloyl group is preferred, and a (meth)acryloyloxy group is more preferred from the viewpoint of reactivity.

[0772] The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds.

[0773] The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above-mentioned ethylenically unsaturated bonds.

[0774] Furthermore, from the perspective of film strength of the resulting pattern (cured film), the photosensitive resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical crosslinking agent. The compound having three or more ethylenically unsaturated bonds is preferably a compound having 3 to 15 ethylenically unsaturated bonds, more preferably a compound having 3 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 3 to 6 ethylenically unsaturated bonds.

[0775] Furthermore, the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more groups containing the above-mentioned ethylenically unsaturated bonds, more preferably a compound having 3 to 15 groups, further preferably a compound having 3 to 10 groups, and particularly preferably a compound having 3 to 6 groups.

[0776] Furthermore, from the viewpoint of film strength of the obtained pattern (cured film), the photosensitive resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0777] 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.

[0778] As the specific example of the free radical crosslinking agent, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or its esters, amides can be enumerated, preferably the ester of unsaturated carboxylic acid and polyol compound and the amides of unsaturated carboxylic acid and polyamine compound.In addition, the addition reaction product of unsaturated carboxylic acid ester or amides with nucleophilic substituents such as hydroxyl, amino, thiol and monofunctional or polyfunctional isocyanate or epoxy, and the dehydration condensation reaction product of monofunctional or polyfunctional carboxylic acid etc. can also be preferably used.In addition, the addition reaction product of unsaturated carboxylic acid ester or amides with electrophilic substituents such as isocyanate group or epoxy group and monofunctional or polyfunctional alcohols, amines, thiols is also preferably used, and then the substitution reaction product of unsaturated carboxylic acid ester or amides with dissociation substituents such as halogen group or tosyloxy and monofunctional or polyfunctional alcohols, amines, thiols. Furthermore, as another example, compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used instead of the unsaturated carboxylic acid. For specific examples, reference can be made to paragraphs 0113 to 0122 of JP-A-2016-027357, the contents of which are incorporated herein.

[0779] Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, and polyfunctional alcohols such as glycerol or trimethylolethane to which ethylene oxide or propylene oxide is added and then (meth)acrylated. Esterified compounds, (meth)acrylic acid urethanes described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, polyfunctional acrylates or methacrylates such as epoxy acrylates that are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Examples include 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.

[0780] 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 JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216 can also be used.

[0781] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Application Laid-Open No. 02-025493 can also be cited. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Furthermore, compounds 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.

[0782] In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of WO-2015 / 199219 can also be preferably used, and the contents of these compounds are incorporated into this specification.

[0783] Furthermore, 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 (meth)acrylating the resultant.

[0784] Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical crosslinking agents, and these contents are incorporated into this specification.

[0785] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomers can also be used.

[0786] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, bifunctional methacrylates having four vinyloxy chains, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate having three isobutyleneoxy 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, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.). 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 NOFCORPORATION.), etc.

[0787] Preferred free radical crosslinking agents include urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open 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. Furthermore, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.

[0788] The free radical crosslinking agent may be one having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical crosslinking agents having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical crosslinking agents obtained by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides to obtain acid groups are more preferred. Among the free radical crosslinking agents obtained by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides to obtain acid groups, compounds in which the aliphatic polyhydroxy compounds are pentaerythritol or dipentaerythritol are particularly preferred. Examples of commercially available products include M-510 and M-520, which are polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD.

[0789] The preferred acid value of a free radical crosslinking agent containing an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. A free radical crosslinking agent with an acid value within this range provides excellent workability during production and, consequently, excellent developability. Furthermore, it exhibits good polymerizability. Furthermore, from the perspective of developing speed during alkaline development, the preferred acid value of a free radical crosslinking agent containing an acid group is 0.1 to 300 mgKOH / g, particularly preferably 1 to 100 mgKOH / g. The acid value is measured in accordance with JIS K0070:1992.

[0790] From the perspective of suppressing warpage caused by controlling the elastic modulus of the pattern (cured film), the photosensitive resin composition of the present invention can preferably use a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As the monofunctional free radical crosslinking agent, preferably used are (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, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam; and allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. Monofunctional radical crosslinking agents are preferably compounds having a boiling point of 100° C. or higher at normal pressure to suppress volatilization before exposure. In addition, bifunctional methacrylates or acrylates are also preferably used from the viewpoints of pattern resolution and film stretchability.

[0791] As specific compounds, 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, pentaerythritol diacrylate, pentaerythritol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol Dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid PO-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond. These can be used in combination of two or more as needed.

[0792] When a radical crosslinking agent is present, its content is preferably greater than 0% by mass and less than 60% by mass relative to the total solids content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or greater. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0793] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used simultaneously, the total amount thereof is preferably within the above range.

[0794] <Other cross-linking agents>

[0795] The photosensitive resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0796] In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned free radical cross-linking agents, and are preferably compounds having multiple groups in the molecule that promote the reaction (forming covalent bonds with other compounds in the composition or their reaction products) by the photosensitization of the above-mentioned photosensitizer, and more preferably compounds having multiple groups in the molecule that promote the reaction (forming covalent bonds with other compounds in the composition or their reaction products) by the action of an acid or a base.

[0797] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator as a photosensitizer in an exposure step such as the first area exposure step or the second area exposure step.

[0798] As other crosslinking agents, compounds having at least one group selected from a hydroxymethyl group and an alkoxymethyl group are preferred, and compounds having a structure in which at least one group selected from a hydroxymethyl group and an alkoxymethyl group is directly bonded to a nitrogen atom are more preferred.

[0799] Other crosslinking agents include, for example, compounds having a structure obtained by reacting amino-containing compounds such as melamine, acetylene carbamide, urea, alkylene urea, and benzoguanamine with formaldehyde, or by reacting formaldehyde with an alcohol, with the hydrogen atoms of the amino groups being substituted with hydroxymethyl or alkoxymethyl groups. The methods for producing these compounds are not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. Furthermore, these compounds may be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds.

[0800] As the above-mentioned amino-containing compound, a cross-linking agent using melamine is referred to as a melamine-based cross-linking agent, a cross-linking agent using acetylene carbamide, urea or alkylene urea is referred to as a urea-based cross-linking agent, a cross-linking agent using alkylene urea is referred to as an alkylene urea-based cross-linking agent, and a cross-linking agent using benzoguanamine is referred to as a benzoguanamine-based cross-linking agent.

[0801] Among these, the photosensitive resin composition of the present invention preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0802] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0803] Specific examples of the urea-based crosslinking agent include monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide;

[0804] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[0805] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated 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,

[0806] Propylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated 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,

[0807] 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0808] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated 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.

[0809] Furthermore, as the compound having at least one group selected from a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0810] Specific examples of such compounds include p-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, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetris[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.

[0811] As other cross-linking agents, commercially available products can be used. Preferred commercially available 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, and 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, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

[0812] Furthermore, the photosensitive resin composition of the present invention preferably contains at least one compound selected from epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0813] [Epoxy compounds (compounds having an epoxy group)]

[0814] Epoxy compounds are preferably compounds having two or more epoxy groups per molecule. Epoxy groups undergo crosslinking reactions at temperatures below 200°C, and since dehydration reactions associated with crosslinking do not occur, film shrinkage is less likely to occur. Therefore, the inclusion of epoxy compounds effectively suppresses low-temperature curing and warping of the photosensitive resin composition.

[0815] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, preferably 2 to 15 repeating units.

[0816] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited to these. Specific examples include 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 ( EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (these are trade names, DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (these are trade names, NewJapan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (trade names, manufactured by DAICEL CORPORATION), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[0817] [Oxetane compounds (compounds having an oxetane group)]

[0818] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (e.g., OXT-121, OXT-221, OXT-191, OXT-223). These compounds may be used alone or in combination of two or more.

[0819] [Benzoxazine compounds (compounds having a benzoxazolyl group)]

[0820] Benzoxazine compounds are preferred because they do not generate outgassing during curing due to a cross-linking reaction derived from a ring-opening addition reaction, and further reduce thermal shrinkage to suppress the occurrence of warping.

[0821] Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine, Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0822] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solids content of the photosensitive resin composition of the present invention. The other crosslinking agent may be present alone or in combination. When two or more other thermal crosslinking agents are present, their total amount is preferably within the above range.

[0823] <Compounds having a sulfonamide structure, compounds having a thiourea structure>

[0824] From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the photosensitive resin composition of the present invention preferably further contains at least one compound selected from compounds having a sulfonamide structure and compounds having a thiourea structure.

[0825] [Compounds with a sulfonamide structure]

[0826] The sulfonamide structure is represented by the following formula (S-1).

[0827] [Chemical Formula 48]

[0828]

[0829] 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. * each independently represents a bonding site with other structures.

[0830] The above R is preferably the same as R in the following formula (S-2) 2 Same group.

[0831] The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

[0832] The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

[0833] [Chemical Formula 49]

[0834]

[0835] In formula (S-2), R 1 、R 2 and R 3 Each independently represents a hydrogen atom or a monovalent organic group, R 1 、R 2 and R 3 Two or more of them may be bonded to each other to form a ring structure.

[0836] R 1 、R 2 and R 3 Each independently is preferably a monovalent organic group.

[0837] As R 1 、R 2 and R 3 Examples of the group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these groups.

[0838] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.

[0839] The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0840] The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0841] The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

[0842] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.

[0843] 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, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a triazine ring.

[0844] Among these, R 1 is an aryl group and R 2 and R 3 A compound in which each is independently a hydrogen atom or an alkyl group.

[0845] 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-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[0846] 〔Compounds with thiourea structure〕

[0847] The thiourea structure is a structure represented by the following formula (T-1).

[0848] [Chemical Formula 50]

[0849]

[0850] In formula (T-1), R 4 and R 5 Each independently represents a hydrogen atom or a monovalent organic group, R 4 and R 5 Can bond to form a ring, R 4 It can form a ring structure by bonding with other structures bonded by *. 5 It may bond with other structures bonded with * to form a ring structure, and * each independently represents a bonding site with other structures.

[0851] R 4 and R 5 Each independently preferably represents a hydrogen atom.

[0852] As R 4 and R 5 Examples of the group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these groups.

[0853] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.

[0854] The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0855] The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0856] The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

[0857] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.

[0858] 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, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a triazine ring.

[0859] The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

[0860] The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

[0861] [Chemical Formula 51]

[0862]

[0863] In formula (T-2), R 4 ~R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 4 ~R 7At least two of them may be bonded to each other to form a ring structure.

[0864] In formula (T-2), R 4 and R 5 The meaning is the same as R in formula (T-1) 4 and R 5 Same, preferred method is also the same.

[0865] In formula (T-2), R 6 and R 7 Each independently is preferably a monovalent organic group.

[0866] In formula (T-2), R 6 and R 7 The preferred embodiment of the monovalent organic group in formula (T-1) is the same as R 4 and R 5 The preferred embodiment of the monovalent organic group is the same as that of

[0867] Examples of the compound 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-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[0868] 〔content〕

[0869] 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 even more preferably 0.2 to 3 mass %.

[0870] The photosensitive resin composition of the present invention may contain only one compound selected from compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more compounds. When containing only one compound, the content of the compound is preferably within the above range. When containing two or more compounds, the total amount thereof is preferably within the above range.

[0871] Migration inhibitors

[0872] The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the transfer of metal ions originating from the metal layer (metal wiring) into the photocurable layer.

[0873] Migration inhibitors are not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas, compounds having a sulfhydryl group, 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.

[0874] Alternatively, an ion capture agent that captures anions such as halogen ions may be used.

[0875] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compound described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of JP-A-2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015 / 199219 can be used.

[0876] Specific examples of the migration inhibitor include the following compounds.

[0877] [Chemical Formula 52]

[0878]

[0879] 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.

[0880] The migration inhibitor may be one or two or more. When two or more migration inhibitors are used, the total amount thereof is preferably within the above range.

[0881] <Polymerization inhibitor>

[0882] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

[0883] As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, 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 can be preferably used. , 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine cerium 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-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO-2015 / 125469 can also be used.

[0884] Furthermore, the following compounds (Me is a methyl group) can be used.

[0885] [Chemical Formula 53]

[0886]

[0887] 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% by mass, more preferably 0.01 to 5% by mass, further preferably 0.02 to 3% by mass, and particularly preferably 0.05 to 2.5% by mass relative to the total solid content of the photosensitive resin composition of the present invention.

[0888] The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0889] <Metal Adhesion Improver>

[0890] The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[0891] Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015 / 199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011 / 080992, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014 / 097594. Furthermore, it is also preferred to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. Furthermore, the following compounds are also preferably used as silane coupling agents: In the following formula, Et represents an ethyl group.

[0892] [Chemical Formula 54-1]

[0893]

[0894] Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used. Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylenediaminetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl 1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0895] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and diisopropylaluminum ethyl acetoacetate.

[0896] 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 even more 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 better, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become better. The metal adhesion improver may be only one or two or more. When two or more are used, their total is preferably within the above range.

[0897] <Sensitizer>

[0898] The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific activating radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, electron transfer, energy transfer, and heat generation occur. This chemically changes the thermal radical polymerization initiator or the photoradical polymerization initiator, causing it to decompose and generate free radicals, acids, or bases.

[0899] Examples of the sensitizer include 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-dimethylaminophenylallyl indanone, p- Dimethylaminobenzylidene 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, -Ethoxycarbonyl-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-morpholinobenzophenone, isoamyl dimethylaminobenzoate Ester, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0900] Furthermore, a sensitizing dye may be used as the sensitizer.

[0901] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

[0902] When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass relative to the total solids content of the photosensitive resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[0903] <Other additives>

[0904] The photosensitive resin composition of the present invention may contain various additives as needed, such as surfactants, chain transfer agents, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, and aggregation inhibitors, within a range that can achieve the effects of the present invention. When these additives are added, their total amount is preferably 3% by mass or less based on the solid content of the photosensitive resin composition.

[0905] 〔Surfactant〕

[0906] From the perspective of further improving coating properties, various surfactants can be added to the photosensitive resin composition of the present invention. As surfactants, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferred. In the following formula, the brackets representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the brackets representing the repeating units of the side chains represent the number of repetitions of each repeating unit.

[0907] [Chemical Formula 54-2]

[0908]

[0909] Furthermore, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015 / 199219 can also be used.

[0910] 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, and RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, and Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, and 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. Fluorine-based surfactants that can be used include compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503. As the fluorine-based surfactant, a block polymer can also be used. Specific examples include compounds described in JP-A-2011-89090.

[0911] Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds containing the following repeating units: repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups).

[0912] Fluorine-based surfactants include fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0913] 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. Fluorine-based surfactants with a fluorine content within this range are effective in achieving uniformity in the thickness of the coating film and in terms of liquid conservation, and also have good solubility in the composition.

[0914] Examples of the silicone 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.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

[0915] Examples of the hydrocarbon surfactant 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.).

[0916] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, 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 esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Boyd & Moore Executive Search), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.). Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), etc.

[0917] Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0918] Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.) and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

[0919] When the photosensitive resin composition of the present invention includes a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solids content of the photosensitive resin composition of the present invention. The surfactant may be a single surfactant or two or more surfactants. When two or more surfactants are present, the total amount thereof is preferably within the above range.

[0920] Chain transfer agent

[0921] 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. Examples of chain transfer agents include compounds containing SH, PH, SiH, and GeH within their molecules. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonating them through oxidation. In particular, thiol compounds are preferably used.

[0922] Furthermore, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used.

[0923] 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 solids content of the photosensitive resin composition of the present invention. The chain transfer agent may be a single type or two or more types. When two or more chain transfer agents are used, the total amount thereof is preferably within the above range.

[0924] [Higher fatty acid derivatives]

[0925] In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention so that the derivative is localized on the surface of the photosensitive resin composition during the drying process after coating.

[0926] Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used.

[0927] 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% by mass relative to the total solids content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be a single type or two or more types. When two or more types are present, the total amount of the higher fatty acid derivative is preferably within the above range.

[0928] 〔Inorganic particles〕

[0929] 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.

[0930] 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.

[0931] Containing a large amount of inorganic particles may deteriorate the mechanical properties of the cured film. Furthermore, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[0932] 〔UV absorber〕

[0933] The composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.

[0934] Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0935] Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; Bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0936] In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.

[0937] The composition of the present invention may or may not contain a UV absorber. However, when contained, the content of the UV absorber is preferably from 0.001% by mass to 1% by mass, more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid content of the composition of the present invention.

[0938] [Organic titanium compounds]

[0939] The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when the resin composition is cured at a low temperature.

[0940] Examples of the organic titanium compound that can be used include organic titanium compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0941] Specific examples of the organic titanium compound are shown in the following I) to VII).

[0942] I) Titanium chelate compound: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide excellent storage stability for negative-type photosensitive resin compositions and yield good cured patterns. Specific examples include titanium bis(triethanolamine)diisopropoxytitanium, di(n-butoxy)bis(2,4-glutarate)titanium, diisopropoxybis(2,4-glutarate)titanium, diisopropoxybis(tetramethylpimelate)titanium, and diisopropoxybis(ethyl acetoacetate)titanium.

[0943] II) Tetraalkoxytitanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetrakis[bis{2,2-(allyloxymethyl)propoxy}]titanium, and the like.

[0944] III) Titanocene compounds: for example, pentamethylcyclopentadienyltrimethoxytitanium, 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.

[0945] IV) Monoalkoxytitanium compounds: Examples include tris(dioctylphosphate)isopropoxytitanium and tris(dodecylbenzenesulfonate)isopropoxytitanium.

[0946] V) Titanium oxide compound: Examples include bis(glutarate)titanium oxide, bis(tetramethylpimelate)titanium oxide, and titanium phthalocyanine oxide.

[0947] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0948] VII) Titanate coupling agent: for example, isopropyl tridecylbenzenesulfonyl titanate.

[0949] Among these, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, diisopropoxybis(ethyl acetoacetate)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.

[0950] When an organotitanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the cyclized resin precursor. When the amount is 0.05 parts by mass or greater, the resulting cured pattern exhibits excellent 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.

[0951] [Antioxidant]

[0952] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the ductility characteristics of the cured film and the adhesion to the metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, thioether compounds, etc. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. Preferably, it is a compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the aforementioned substituent, preferably, it is a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. In addition, as the antioxidant, it is also preferred to have a compound having a phenol group and a phosphite group in the same molecule. In addition, as the antioxidant, it is also preferred to use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. Examples of commercially available antioxidants include 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, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, as antioxidants, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.

[0953] Furthermore, the composition of the present invention may contain a latent antioxidant as needed. Examples of latent antioxidants include compounds in which the site that functions as an antioxidant is protected by a protecting group, wherein 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. Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219. Commercially available products of latent antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by the following general formula (3).

[0954] [Chemical Formula 54-3]

[0955]

[0956] In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R 6 represents an alkylene group having 2 or more carbon atoms. 7 represents an alkylene group having 2 or more carbon atoms, and a monovalent to tetravalent organic group containing at least one atom selected from an O atom and a N atom. k represents an integer of 1 to 4.

[0957] The compound represented by the general formula (3) suppresses oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins and can suppress metal oxidation by its rust-proofing effect on metal materials.

[0958] In order to be able to act on both the resin and the metal material, k is more preferably an integer of 2 to 4. 7 , examples include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkyl silyl groups, alkoxy silyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among them, alkyl ether and -NH- are preferred from the viewpoints of solubility in developer and metal adhesion, while -NH- is more preferred from the viewpoints of interaction with the resin and metal adhesion due to metal complex formation.

[0959] The compound represented by the following general formula (3) can be exemplified by the following compounds, but is not limited to the following structures.

[0960] [Chemical Formula 54-4]

[0961]

[0962] [Chemical Formula 54-5]

[0963]

[0964] [Chemical Formula 54-6]

[0965]

[0966] [Chemical Formula 54-7]

[0967]

[0968] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. If the amount added is less than 0.1 parts by mass, it is difficult to achieve the ductility characteristics of the cured film and the effect of improving adhesion to metal materials. If the amount added is more than 10 parts by mass, the sensitivity of the resin composition may decrease due to interaction with the photosensitizer. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, the total amount of these antioxidants is preferably within the above range.

[0969] <Regulation on other substances>

[0970] From the viewpoint 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 further preferably less than 0.6 mass %.

[0971] Examples of methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0972] From the perspective of insulation properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are included, the total amount of these metals is preferably within the above range.

[0973] Furthermore, as methods for reducing the amount of metal impurities accidentally contained in the photosensitive resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as the raw materials constituting the photosensitive resin composition of the present invention, filtering the raw materials constituting the photosensitive resin composition of the present invention through a filter, lining the interior of an apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions that minimize contamination.

[0974] Considering its use as a semiconductor material and its resistance to wiring corrosion, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Halogen atoms present as halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or of chlorine ions and bromide ions, is preferably within the above-mentioned ranges.

[0975] As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

[0976] Conventionally known containers can be used as storage containers for the photosensitive resin composition of the present invention. Furthermore, it is also preferred to use a multilayer bottle having an inner wall composed of six layers of six different resins, or a bottle having a seven-layer structure of six different resins, as the storage container to suppress the incorporation of impurities into the raw materials and the photosensitive resin composition. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

[0977] <Applications of the photosensitive resin composition>

[0978] The photosensitive resin composition of the present invention is preferably used to form an interlayer insulating film for a redistribution layer.

[0979] Furthermore, it can also be used to form an insulating film of a semiconductor device, a stress buffer film, or the like.

[0980] <Preparation of Photosensitive Resin Composition>

[0981] 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.

[0982] Furthermore, in order to remove foreign matter such as dust or particles in the photosensitive resin composition, filtration using a filter is preferably performed. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. On the other hand, from the perspective of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter can be a filter that has been pre-cleaned with an organic solvent. In the filtration 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. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a cycle filtration. Furthermore, filtration can be performed after pressurization. When filtering after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, it is preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, and even more preferably 0.05 MPa to 0.7 MPa.

[0983] In addition to filtration using a filter, impurity removal using an adsorbent can also be performed. Filter filtration and impurity removal using an adsorbent can also be combined. Known adsorbents can be used as adsorbents. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[0984] Example

[0985] Hereinafter, the present invention will be further described in detail with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing 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 by mass.

[0986] <Synthesis example 1>

[0987] [Synthesis of polyimide precursor PIP-1]

[0988] In a dry reactor equipped with a stirrer, 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 continuously, and the mixture was stirred at 60°C for 18 hours. The mixture was then cooled to -20°C, and 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, the mixture was heated to room temperature and stirred for 2 hours, followed by the addition of 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to obtain a clear solution. Subsequently, a mixture of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour. Subsequently, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Subsequently, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45° C. under reduced pressure for 3 days to obtain a polyimide precursor PIP-1.

[0989] <Synthesis example 2>

[0990] [Synthesis of polyimide precursor PIP-2]

[0991] In the above-mentioned Synthesis Example 1, except having changed 4,4'-diaminodiphenyl ether into 1,6-diaminohexane in an equimolar amount, the same method as Synthesis Example 1 was carried out to obtain a polyimide precursor PIP-2.

[0992] <Synthesis Example 3>

[0993] [Synthesis of polyimide precursor PIP-3]

[0994] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic 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. The reaction mixture was then cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl2 was added over 10 minutes while maintaining the temperature at -10±4°C. After dilution 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 for 20 minutes. Then, the reaction mixture was stirred at room temperature for 1 night. Then, 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 out, placed in 4 liters of water, stirred again for 30 minutes, and filtered out again. Then, the obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain the polyimide precursor PIP-3.

[0995] <Synthesis Example 4>

[0996] [Synthesis of polyimide PI-1]

[0997] In a dry reactor equipped with a stirrer, 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 moisture. Subsequently, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at 40°C for 2 hours. Next, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40°C for 2 hours. After stirring, the temperature was raised to 180°C while nitrogen was flowing at a rate of 200 ml / min, and the mixture was stirred for 6 hours.

[0998] After the reaction solution was cooled to 25°C, 0.005g of p-methoxyphenol was added and dissolved. 24.82g (160mmol) of 2-isocyanatoethyl methacrylate was added dropwise to the solution, stirred at 25°C for 2 hours, and then stirred at 60°C for 3 hours. It was cooled to 25°C, 10g of acetic acid was added, and stirred at 25°C for 1 hour. After stirring, it was precipitated in 2 liters of water / methanol = 75 / 25 (volume ratio) and stirred at 2,000rpm 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 for 1 day under reduced pressure to obtain polyimide PI-1.

[0999] <Synthesis example 5>

[1000] [Synthesis of polybenzoxazole precursor PBP-1]

[1001] To a three-necked flask equipped with a thermometer, stirrer, and nitrogen inlet tube were added 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. The mixture was stirred at room temperature and then cooled to -15°C in a dry ice / methanol bath. While maintaining the reaction temperature between -5°C and -15°C, a mixed solution of 30.11 g (0.144 mol) of a 30% by mass solution of 1,4-cyclohexanedicarboxylic acid dichloride in NMP, 3.83 g (0.016 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 96.25 g of NMP was added dropwise. After the additions were completed, the resulting mixture was stirred at room temperature for 16 hours.

[1002] The reaction solution was then cooled to below -5°C in an ice / methanol bath. While maintaining the reaction temperature below -0°C, a mixture of 9.59 g (0.090 mol) of butyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34.5 g of NMP was added dropwise. After the addition was complete, the mixture was stirred for a further 16 hours.

[1003] The reaction solution was diluted with 550 g of NMP and added to 4 L of a vigorously stirred mixture of deionized water and methanol (80 / 20 by volume). 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.

[1004] To a 500 mL eggplant-shaped flask, 25.00 g of resin A-1a, 125 g of NMP, and 125 g of methyl ethyl ketone were added and concentrated under reduced pressure at 60°C until the contents reached 160 g. 0.43 g (1.85 mmol) of camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.12 g (0.065 mol) of 2,3-dihydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at room temperature for 1.5 hours. 0.37 g of triethylamine and 150 g of NMP were added to the resulting solution, followed by dilution.

[1005] The resulting solution was added to a vigorously stirred 2 L mixture of deionized water and methanol (80 / 20 by volume). 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 the polybenzoxazole (PBO) precursor PBP-1.

[1006] <Examples and Comparative Examples>

[1007] In each example, the components listed in Tables 1 to 3 below were mixed to obtain a photosensitive resin composition. In the comparative example, the components listed in Table 3 below were mixed to obtain a comparative composition.

[1008] 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. Furthermore, the content of the solvent in each composition was set so that the solid content concentration of the composition would be the values ​​listed in Tables 1 to 3.

[1009] The obtained photosensitive resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore size of 0.8 μm.

[1010] In Tables 1 to 3, "-" indicates that the composition does not contain the component.

[1011] [Table 1]

[1012]

[1013] [Table 2]

[1014]

[1015] [Table 3]

[1016]

[1017] The details of the components described in Tables 1 to 3 are as follows.

[1018] 〔Resin〕

[1019] PIP-1 to PIP-3: PIP-1 to PIP-3 synthesized above

[1020] PI-1: PI-1 synthesized above

[1021] PBP-1: PBP-1 synthesized above

[1022] 〔Free radical crosslinker〕

[1023] B-1: Tetraethylene glycol dimethacrylate

[1024] B-2: Dipentaerythritol hexaacrylate

[1025] ·B-3: LIGHT ESTER BP-6EM (made by KYOEISHA CHEMICAL Co., LTD.)

[1026] ·B-4: SR209 (manufactured by Sartomer Japan Inc.)

[1027] 〔Photosensitive agent〕

[1028] C-1: Irgacure 784 (manufactured by BASF)

[1029] C-2: Irgacure OXE-01 (manufactured by BASF)

[1030] ·C-3: ADEKA NCI-930 (manufactured by ADEKA CORPORATION)

[1031] C-4: Compound with the following structure

[1032] [Chemical Formula 55]

[1033]

[1034] 〔Silane coupling agent〕

[1035] D-1: N-(3-(Triethoxysilyl)propyl)phthalamic acid

[1036] D-2: Benzophenone-3,3'-bis(N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic acid

[1037] ·D-3: IM-1000 (manufactured by JX Nippon Mining & Metals Corporation)

[1038] D-4: N-[3-(Triethoxysilyl)propyl]maleic acid monoamide

[1039] D-5: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[1040] 〔Polymerization inhibitor〕

[1041] E-1: 2-Nitroso-1-naphthol

[1042] E-2: 4-Methoxyphenol

[1043] ·E-3: Compound with the following structure

[1044] ·E-4: 4-Methoxy-1-naphthol

[1045] E-5: p-Benzoquinone

[1046] [Chemical Formula 56]

[1047]

[1048] 〔Sensitizer〕

[1049] F-1: 7-(Diethylamino)coumarin-3-carboxylic acid ethyl ester

[1050] F-2: N-phenyldiethanolamine

[1051] 〔Migration inhibitor〕

[1052] ·G-1: 1H-tetrazole

[1053] 〔Acid crosslinking agent (other crosslinking agents)〕

[1054] ·H-1: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD)

[1055] [Thermal acid generator]

[1056] I-1: Isopropyl p-toluenesulfonate

[1057] 〔additive〕

[1058] J-1: 1,3-Dibutylthiourea

[1059] [Thermal alkali generator]

[1060] K-1: Compound with the following structure

[1061] [Chemical Formula 57]

[1062]

[1063] 〔Surfactant〕

[1064] L-1: F-554 (manufactured by DIC Corporation)

[1065] Solvent

[1066] S-1: N-methyl-2-pyrrolidone

[1067] S-2: Ethyl lactate

[1068] S-3: γ-butyrolactone

[1069] S-4: dimethyl sulfoxide

[1070] In Tables 1 to 3, the description in the "Ratio" column indicates the content (mass %) of each solvent relative to the total mass of the solvent.

[1071] <Evaluation>

[1072] [Evaluation of pattern shape]

[1073] In each of the Examples and Comparative Examples, each photosensitive resin composition or comparative composition was applied (coated) in a layer form on a silicon wafer by spin coating to form each photosensitive film.

[1074] In each of the Examples and Comparative Examples, the silicon wafer using the photosensitive film was dried on a hot plate at 80° C. for 3 minutes to form a photosensitive film having the thickness described in the “Film Thickness (μm)” column of Tables 1 to 3 on the silicon wafer.

[1075] 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 in Tables 1 to 3. For example, in Example 1, all four exposures were performed with a laser output of 0.6 W. Furthermore, in Example 20, the first area exposure process was performed with an output of 0.6 W, the second area exposure process was performed with an output of 1.2 W, the third area exposure process was performed with an output of 1.8 W, and the fourth area exposure process was performed with an output of 1.8 W. Furthermore, in the example where "HP" is described in the "Exposure Wavelength (nm)" column, exposure was performed using a high-pressure mercury lamp.

[1076] Exposures were performed at the times listed in the "Number of Exposures" column and the intervals listed in the "Interval (seconds)" column in Tables 1 to 3. For example, in Example 1, a total of four exposures (quadruple exposures) were performed with intervals of 10 seconds (times during which no exposure was performed). Furthermore, in Example 5, a total of four exposures were performed with the intervals changed to 5 seconds, 10 seconds, and 15 seconds.

[1077] In each example or comparative example, each exposure step was performed with the same exposure dose. When a high-pressure mercury lamp was used for exposure, the above exposure dose was defined as the i-ray exposure dose.

[1078] Exposure was performed through a mask (a binary mask having a pattern of 1:1 line and space and a line width of 20 μm).

[1079] After the above exposure, in the examples listed as "A" in the "Developer Solution" column of Tables 1 to 3, development was performed with cyclopentanone for 60 seconds and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds to obtain a line-and-space pattern on the photosensitive film. In the examples listed as "B" in the "Developer Solution" column of Tables 1 to 3, development was performed with a 2.5% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water for 20 seconds to obtain a line-and-space pattern on the exposed photosensitive film. In Example 11, the above development was performed after heating on a hot plate at 100°C for 60 seconds.

[1080] Afterwards, the developed pattern and the silicon wafer having the pattern formed thereon were heated at a heating rate of 10°C / min in a nitrogen atmosphere until the temperature reached the temperature listed in the "Curing Temperature (°C)" column of Tables 1 to 3. The temperature was then cured for the time listed in the "Curing Time (min)" column of Tables 1 to 3, thereby obtaining a silicon wafer having the pattern formed thereon.

[1081] 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 a cross-section of the pattern. The cross-section of the line-and-space pattern was observed at a magnification of 200x using an optical microscope to evaluate the cross-sectional shape of the pattern.

[1082] Specifically, in each example 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 evaluated according to the following evaluation criteria. It can be said that the closer the taper angle is to 90°, the better the pattern shape.

[1083] -Evaluation Criteria-

[1084] A: The taper angle is 85° or more and 95° or less.

[1085] B: The taper angle is 80° or more and less than 85°, or more than 95° and less than 100°.

[1086] C: Cone angle is less than 80° or more than 100°.

[1087] 〔Resolution Evaluation〕

[1088] In each of the Examples and Comparative Examples, a photosensitive film having a thickness described in the "Film Thickness (μm)" column of Tables 1 to 3 was formed on a silicon wafer by the same method as that for evaluating the pattern shape.

[1089] The photosensitive film formed on the silicon wafer was exposed in the same manner as in the evaluation of the pattern shape, except that a photomask having a line and space pattern with 1 μm graduations between 5 μm and 25 μm was used.

[1090] After the exposure, each photosensitive film was developed and heated in the same manner as in the evaluation of the pattern shape, thereby obtaining a silicon wafer having a pattern formed thereon.

[1091] The pattern after development was observed using a scanning electron microscope (SEM) to determine the minimum line width.

[1092] Evaluation was performed 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, the better the resolution.

[1093] -Evaluation Criteria-

[1094] A: Minimum line width is less than 10μm

[1095] B: Minimum line width is 10μm or more and less than 20μm

[1096] C: A pattern having a minimum line width of 20 μm or more or having a line width (having edge sharpness) could not be obtained.

[1097] The pattern forming method of Comparative Example 1 performs only one exposure step without a second exposure step. In this example, it is found that the pattern shape is not good.

[1098] <Example 101>

[1099] The photosensitive resin composition used in Example 1 was applied to the surface of the copper thin layer of a resin substrate having a copper thin layer formed on the surface by spin coating. The layer was dried at 80°C for 3 minutes to form a 20 μm thick photocurable layer. The layer was then exposed four times with a 0.6W semiconductor laser at 10-second intervals (without exposure). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-space pattern and a line width of 10 μm). After exposure, the layer was developed with cyclopentanone for 60 seconds and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds to obtain a layer pattern.

[1100] Next, the temperature was raised at a rate of 10°C / min in a nitrogen atmosphere to 230°C and then maintained at that temperature for 120 minutes for curing, thereby forming a redistribution layer interlayer insulating film having excellent insulation properties.

[1101] Furthermore, semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, and normal operation was confirmed.

Claims

1. A pattern forming method, comprising: A first region exposure step of selectively exposing a first region, which is a portion of the photosensitive film formed of the photosensitive resin composition; A second area exposure step of selectively exposing a portion of the photosensitive film after the first area exposure step, namely, a second area; and A developing step is to develop the photosensitive film after the second region exposure step. At least a portion of the area included in the first area and at least a portion of the area included in the second area are a common area, The ratio of the area of ​​the region included in both the first region and the second region to the total area of ​​the first region is 50 to 100%. The photosensitive resin composition comprises at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor, and a photosensitizer. The photosensitizer is a photo-radical polymerization initiator or a photoacid generator, When the photosensitizer is a photoradical polymerization initiator, the resin has a radical polymerizable group, and the photosensitive resin composition further contains a radical crosslinking agent. In addition, when the photosensitizer is a photoacid generator, the resin has an acid-decomposable group. In the step of exposing a partial region of the photosensitive film before the development step, the time from the end of a certain exposure step to the start of another exposure step excluding the other exposure steps is 0.1 seconds or longer.

2. The pattern forming method according to claim 1, comprising: a third region exposure step of selectively exposing a portion of the photosensitive film after the second region exposure step, i.e., a third region; and The fourth area exposure step is to selectively expose a portion of the photosensitive film after the third area exposure step, that is, the fourth area. The development process is a process for developing the photosensitive film after the exposure process of the fourth area, 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 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.

3. The pattern forming method according to claim 1 or 2, wherein: The exposure wavelength in the first region exposure step and the second region exposure step is 300 nm to 450 nm.

4. The pattern forming method according to claim 1 or 2, wherein The photosensitive film composed of the photosensitive resin composition has a thickness of 10 μm or more.

5. The pattern forming method according to claim 1 or 2, wherein: The development in the development step is performed using an organic solvent as a developing solution.

6. The pattern forming method according to claim 1 or 2, wherein: The resin is a polyimide precursor.

7. The pattern forming method according to claim 1 or 2, wherein: The photosensitive resin composition further includes a sensitizer. 8 . A method for producing a laminate, comprising the pattern forming method according to claim 1 . 9 . A method for manufacturing an electronic device, comprising the pattern forming method according to claim 1 . 10 . A method for manufacturing an electronic device, comprising the method for manufacturing a laminate according to claim 8 .

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