Pattern forming method, photocurable resin composition, method for manufacturing a laminate, and method for manufacturing an electronic device

Abstract

The present application provides a pattern forming method, a photocurable resin composition used in the pattern forming method, a manufacturing method of a laminate including the pattern forming method, and a manufacturing method of an electronic device including the pattern forming method or a photocurable resin composition, the pattern forming method including: a first exposure step of exposing a part of a photocurable film formed of a photocurable resin composition; a development step of developing the photocured film after the exposure by a developer to obtain a developed pattern; and a second exposure step of exposing the developed pattern to obtain a pattern, the photocurable resin composition having a specific composition.

Description

TECHNICAL FIELD

[0001] The present application relates to a pattern forming method, a photocurable resin composition, a manufacturing method of a laminate, and a manufacturing method of an electronic device. BACKGROUND

[0002] Resins such as polyimide and polybenzoxazole are excellent in heat resistance, insulating properties, and the like, and thus can be used for various purposes. The above-mentioned purposes are not particularly limited, but if actual mounting electronic devices are taken as an example, cases where a pattern containing these resins is used as a material for an insulating film or a sealing material or a protective film, and the like, can be cited. Also, the pattern containing these resins is used as a base film or a cover film of a flexible substrate, and the like.

[0003] For example, in the above-mentioned purposes, resins such as polyimide and polybenzoxazole are used in the form of a photocurable resin composition containing these resins.

[0004] For example, by applying these photocurable resin compositions to a substrate by coating or the like, and then performing exposure, development, heating, and the like as necessary, a cured resin can be formed on the substrate.

[0005] The photocurable resin composition can be applied by a known coating method or the like, and thus it can be said that the manufacturing adaptability is excellent in terms of, for example, freedom in design of the shape, size, application position, and the like of the applied photocurable resin composition. From the viewpoint that these resins are excellent in manufacturing adaptability in addition to the high performance possessed by polyimide and polybenzoxazole and the like, the application of the photocurable resin composition containing these resins to industry is expected to expand further.

[0006] For example, in Patent Literature 1, a photosensitive resin composition is described, which is characterized by containing a polyimide precursor having a specific structure, a photobase generator that generates a base by irradiation of actinic rays, and a solvent, and the above-mentioned photobase generator generates a secondary amine having at least one substituent at an α position by irradiation of actinic rays.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT LITERATURE

[0009] Patent Literature 1: Japanese Patent Application Laid-Open No. 2006-189591 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] Conventionally, a photocurable resin composition containing polyimide or polybenzoxazole is applied to a substrate, a developed pattern is formed based on exposure development, and then heating is performed to obtain a pattern.

[0012] Here, sometimes the pattern after heating shrinks with respect to the developed pattern obtained after development.

[0013] An object of the present application is to provide a pattern forming method that suppresses shrinkage of a formed pattern, a photocurable resin composition used in the above pattern forming method, a manufacturing method of a laminate including the above pattern forming method, and a manufacturing method of an electronic device including the above pattern forming method.

[0014] Further, an object of the present application is to provide a novel photocurable resin composition.

[0015] Means for solving technical problems

[0016] Hereinafter, examples of representative embodiments of the present application will be shown.

[0017] <1> A pattern forming method comprising:

[0018] a first exposure step of exposing a part of a photocurable film formed from a photocurable resin composition;

[0019] a development step of developing the above photocurable film after the above exposure by a developing solution to obtain a developed pattern; and

[0020] a second exposure step of exposing the above developed pattern to obtain a pattern,

[0021] the above photocurable resin composition comprises:

[0022] at least one resin selected from a polyimide precursor and a polybenzoxazole precursor;

[0023] a photosensitive compound A having sensitivity to an exposure wavelength in the above first exposure step; and

[0024] a photosensitive compound B having sensitivity to an exposure wavelength in the above second exposure step,

[0025] the above photosensitive compound A is a compound that changes solubility of the above photocurable film with respect to the above developing solution in the above first exposure step,

[0026] at least one of the above photosensitive compound A and the above photosensitive compound B is a photo-base generator.

[0027] <2> The pattern forming method according to <1>, wherein

[0028] the above photosensitive compound A is a compound that generates radicals by the above first exposure step.

[0029] <3> The pattern forming method according to <1> or <2>, wherein

[0030] The photosensitive compound A is a compound that generates an acid by the first exposure process.

[0031] <4> The pattern forming method according to any one of <1> to <3>, wherein

[0032] The photosensitive compound B is a compound that generates a base by the second exposure process.

[0033] <5> The pattern forming method according to any one of <1> to <4>, wherein

[0034] The second exposure process includes exposure to light including light having a wavelength different from the wavelength of the light used in the first exposure process.

[0035] <6> The pattern forming method according to any one of <1> to <5>, wherein

[0036] The temperature in the second exposure process is 50 to 200°C.

[0037] <7> A photocurable resin composition used in the pattern forming method according to any one of <1> to <6>.

[0038] <8> A photocurable resin composition comprising:

[0039] at least one resin selected from a polyimide precursor and a polybenzoxazole precursor;

[0040] a photosensitive compound A; and

[0041] a photosensitive compound B,

[0042] The photosensitive compound A is a compound that can change the solubility of the resin by photosensitivity,

[0043] At least one of the photosensitive compound A and the photosensitive compound B is a photo-base generator,

[0044] The difference between the maximum absorption wavelength of the photosensitive compound A and the maximum absorption wavelength of the photosensitive compound B is 100 nm or more.

[0045] <9> A method for manufacturing a laminate, including the pattern forming method according to any one of <1> to <6>.

[0046] <10> A method for manufacturing an electronic device, including the pattern forming method according to any one of <1> to <6> or the method for manufacturing a laminate according to <9>.

[0047] Effects of the Invention

[0048] According to the present invention, a pattern forming method for suppressing shrinkage of the formed pattern, a photocurable resin composition used in the above pattern forming method, a method for manufacturing a laminate including the above pattern forming method, and a method for manufacturing an electronic device including the above pattern forming method can be provided.

[0049] Furthermore, according to the present invention, a novel photocurable resin composition can be provided. Detailed Implementation

[0050] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments shown.

[0051] In this specification, the numerical range indicated by the “~” symbol represents the range included by the values ​​recorded before and after the “~” as the lower limit and upper limit, respectively.

[0052] In this specification, the term "process" not only refers to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the desired function of the process can be achieved.

[0053] Regarding the designation of groups (atomic groups) in this specification, the designations for unsubstituted and unsubstituted groups (atomic groups) include both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0054] In this manual, unless otherwise specified, "exposure" includes exposure using light, as well as exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation.

[0055] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either one; “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either one; and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either one.

[0056] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0057] In this specification, total solids content represents the total mass of the components after removing the solvent from the total composition. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0058] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are based on gel permeation chromatography (GPC determination) and are defined as polystyrene equivalents. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, these molecular weights are assumed to be those determined using THF (tetrahydrofuran) as the eluent. Furthermore, unless otherwise specified, detection in GPC determinations uses a UV (ultraviolet) detector at a wavelength of 254 nm.

[0059] However, in cases of low solubility or when THF is unsuitable as an eluent, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, detection in GPC assays uses a 254nm UV (ultraviolet) detector.

[0060] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it simply means that there are other layers above or below the reference layer in the multilayer of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, but the reference layer does not need to be in contact with the other layers. Furthermore, unless otherwise specified, the direction of the stacked layers relative to the substrate is referred to as "upper," or, when a photocurable film is present, the direction from the substrate toward the photocurable film is referred to as "upper," and the opposite direction is referred to as "lower." In addition, these vertical and vertical directions are set for convenience in this specification, and in practice, the "upper" direction in this specification may also be different from the vertical direction.

[0061] In this specification, unless otherwise specified, each component included in the composition may contain two or more compounds conforming to that component. Furthermore, unless otherwise specified, the content of each component in the composition represents the total content of all compounds conforming to that component.

[0062] Unless otherwise specified, the temperature in this instruction manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0063] In this specification, the preferred combination of methods is a more preferred method.

[0064] (Pattern Formation Method)

[0065] The pattern forming method of the present invention includes: a first exposure step, exposing a portion of a photocurable film formed by a photocurable resin composition; a developing step, developing the exposed photocurable film with a developing solution to obtain a developed pattern; and a second exposure step, exposing the developed pattern to obtain a pattern, wherein the photocurable resin composition comprises at least one resin selected from polyimide precursor and polybenzoxazole precursor, a photosensitive compound A sensitive to the exposure wavelength in the first exposure step, and a photosensitive compound B sensitive to the exposure wavelength in the second exposure step, wherein the photosensitive compound A is a compound that causes a change in the solubility of the photocurable film relative to the developing solution in the first exposure step, and at least one of the photosensitive compound A and the photosensitive compound B is a photoalkali-generating agent.

[0066] Hereinafter, at least one resin selected from polyimide precursors and polybenzoxazole precursors will also be referred to as "specific resin".

[0067] The pattern forming method of the present invention can suppress shrinkage of the obtained pattern relative to the above-described developed pattern.

[0068] The mechanism by which the above effects are achieved is not yet clear, but the following can be speculated.

[0069] In conventional pattern forming methods, a film composed of a photocurable resin composition containing precursors such as polyimide precursors and polybenzoxazole precursors is exposed once, and then developed to form a developed pattern. The precursors are cyclized by heating the developed pattern.

[0070] Furthermore, Patent Document 1 describes a method in which, in addition to the aforementioned precursor, a film composed of a composition containing a photopolymerization initiator and a photoalkali-generating agent is exposed once to expose both the photopolymerization initiator and the photoalkali-generating agent to light, followed by development and heating to cyclize the precursor and obtain a pattern.

[0071] The inventors have discovered that when a developed pattern is exposed once as described above and then ringed by heating, film shrinkage sometimes occurs before and after heating.

[0072] Therefore, the inventors discovered and completed the present invention as follows: a photosensitive film formed from two photosensitive compounds, at least one of which is a photoalkali-generating agent, is subjected to a first exposure step, a development step, and a second exposure step in sequence, and curing based on the photoalkali-generating agent and chemical changes based on the photoacid-generating agent, free radical polymerization initiator, etc., through other exposures, thereby suppressing the shrinkage of the obtained pattern before and after cyclization.

[0073] This can be presumably because the cyclization of the specific resin is achieved through at least two exposures: one for cyclization based on a photo-alkali-generating agent and the other for the aforementioned chemical change. For example, if no heating is performed after the second exposure step, shrinkage based on heating will not occur; and if heating is performed after the second exposure step, cyclization has already occurred in the film, thus suppressing shrinkage based on heating. Furthermore, if heating is performed after the second exposure step, the heating temperature is set to a lower temperature compared to curing the pattern solely by heating, thereby also suppressing shrinkage of the pattern based on heating.

[0074] It can be inferred that, according to the pattern forming method of the present invention, by suppressing the shrinkage of the pattern, deformations such as warping of the pattern can sometimes also be suppressed.

[0075] The photocurable film used in the pattern forming method of the present invention can be a negative photocurable film or a positive photocurable film.

[0076] Positive photocurable film refers to a photocurable film whose exposed portion (exposed portion) is removed by developing solution, while negative photocurable film refers to a photocurable film whose unexposed portion (non-exposed portion) is removed by developing solution.

[0077] Here, when the photocurable film is a negative photocurable film and crosslinking with the crosslinking agent (described later) is performed in the first exposure step, compared to the case where, for example, crosslinking of the crosslinking agent and cyclization of a specific resin are performed simultaneously in a single exposure as described in Patent Document 1 above, the crosslinking reaction of the crosslinking agent is less likely to be hindered by cyclization, thus resulting in an advantageous effect such as a higher final crosslinking density in the pattern. As mentioned above, it is difficult for the chemical solution to penetrate into a pattern with a high crosslinking density, therefore, it is considered to have excellent chemical resistance, for example.

[0078] Specifically, it is believed that patterns can be obtained that suppress the solubility and dispersibility of polar solvents such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH), or mixtures of the above-mentioned polar solvents and the above-mentioned alkaline aqueous solutions.

[0079] As described above, the excellent chemical resistance of the pattern provides the following advantages: for example, when applying other compositions containing solvents to the pattern formed by the pattern forming method of the present invention and curing them to produce a laminate, the dissolution of the pattern can be suppressed even when the pattern comes into contact with a developer or other composition, and the dissolution, dispersion or modification of the pattern can be suppressed even when the pattern comes into contact with a chemical such as a solvent or in an atmosphere in which a chemical such as a solvent is present.

[0080] Furthermore, when the photocurable film is positive, pattern formation for the cyclization precursor cannot be performed, for example, in the manner described in Patent Document 1 above, where the photoalkali-generating agent and other photosensitive compounds are exposed simultaneously. That is, according to the method of the present invention, positive patterns can be formed.

[0081] Furthermore, the pattern forming method of the present invention may include at least a first exposure step, a developing step, and a second exposure step in the aforementioned order. For example, the pattern forming method of the present invention may also include performing multiple first exposure steps before the developing step, performing exposure based on the same light source as the first exposure step (e.g., full-area exposure) during or after the second exposure step following the developing step, or performing multiple second exposure steps after the developing step, etc.

[0082] The pattern forming method of the present invention will now be described in detail.

[0083] <First Exposure Process>

[0084] The pattern forming method of the present invention includes a first exposure step of exposing a portion of a photocurable film formed from a photocurable resin composition.

[0085] In the first exposure step, the photosensitive compound A is exposed to light, and the solubility of the aforementioned photocurable film relative to the developer changes.

[0086] Specifically, for example, if the photosensitive compound A is a photopolymerization initiator or photoacid generator described later, and a particular resin contains a crosslinking group or the photocurable film contains a crosslinking agent or both, crosslinking is performed in the photocurable film, and the solubility of the photocurable film relative to the developer decreases after the first exposure step.

[0087] For example, when photosensitive compound A is the photoacid generator described later, and the developer is the alkaline developer described later, acid is generated in the photocurable film, increasing its solubility relative to the developer.

[0088] For example, when photosensitive compound A is the photoacid generator described later, and the developer is the organic solvent described later, acid is generated in the photocurable film, and its solubility relative to the developer decreases.

[0089] For example, when the photosensitive compound A is a photoalkali-generating agent described later, the cyclization of a specific resin in the photocurable film reduces its solubility relative to the developer.

[0090] As described above, in the first exposure step, for example, the photosensitive compound A can promote the bonding reaction between the crosslinking groups contained in a specific resin or crosslinking agent and other groups, thereby changing the solubility of the photocurable film relative to the developer. Alternatively, the solubility of the photocurable film relative to the developer can be changed by the products generated based on the photosensitive chemical change of the photosensitive compound A. Alternatively, the solubility of the photocurable film relative to the developer can be changed by the cyclization of a specific resin.

[0091] The exposure wavelength in the first exposure step can be appropriately set as the wavelength in which the photosensitive compound A described later has sensitivity, preferably 190 to 1,000 nm, more preferably 200 to 550 nm, and even more preferably 200 to 450 nm.

[0092] Regarding the exposure wavelength, if explained in relation to the light source, examples include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h rays (wavelength 405nm), i rays (wavelength 365nm), and wide (gamma, h, i rays with three wavelengths), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), and (6) electron beams, etc.

[0093] Among these, the light source in the first exposure step is preferably an excimer laser, i-rays, or h-rays. This results in particularly high exposure sensitivity.

[0094] When the maximum absorption wavelengths of photosensitive compound A and photosensitive compound B are different, filters that remove specific wavelengths can be used in these light sources to suppress the photosensitivity of photosensitive compound B.

[0095] Examples of methods for exposing a portion of the photocurable film in the first exposure step include exposure methods using a known photomask and exposure methods for exposing a portion of the photocurable film by laser exposure.

[0096] In the pattern forming method of the present invention, the exposure amount in the first exposure step is calculated as the exposure energy at the wavelength where the photosensitive compound A has sensitivity, and is preferably 100 to 10,000 mJ / cm. 2 More preferably 200–8,000 mJ / cm 2 .

[0097] <Post-exposure heating process>

[0098] The pattern forming method of the present invention may include a step of heating the photocurable film after exposure (post-exposure heating step) after the first exposure step and before the development step described above.

[0099] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0100] The heating time in the post-exposure heating process is preferably 1 minute to 300 minutes, more preferably 5 minutes to 120 minutes.

[0101] Regarding the heating rate in the post-exposure heating process, the rate from the initial heating temperature to the maximum heating temperature is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0102] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0103] There are no particular limitations on the heating mechanism used in the post-exposure heating process; commonly known heating plates, ovens, infrared heaters, etc., can be used.

[0104] Furthermore, during heating, it is preferable to use inert gases such as nitrogen, helium, or argon to conduct the heating in an atmosphere with a low oxygen concentration.

[0105] <Membrane Formation Process>

[0106] The pattern forming method of the present invention may include a film forming step of forming a photocurable film from a photocurable resin composition.

[0107] The photocurable film in the first exposure process can be a photocurable film formed by a film forming process, or a photocurable film obtained by purchasing or other methods.

[0108] The preferred film forming process is a process in which a photocurable resin composition is applied to a substrate to form a film (layered) and obtain a photocurable film.

[0109] <Preparation of Resin Compositions>

[0110] The 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 carried out using conventionally known methods.

[0111] Mixing can be achieved through methods such as mixing based on stirring blades, mixing based on ball milling, and mixing by rotating the tank itself.

[0112] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0113] Furthermore, for the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration using a filter is preferred. Examples of filter pore sizes include, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. Filters that have been pre-cleaned with an organic solvent can be used. In the filtration process, multiple filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes or materials can be combined. For example, a connection method can be described as connecting an HDPE filter with a 1 μm pore size in series as the first stage and an HDPE filter with a 0.2 μm pore size in series as the second stage. Furthermore, various materials can be filtered multiple times. Multiple filtrations can be performed as circulating filtration. Furthermore, filtration can be performed after pressurization. When pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0114] In addition to filtration using filters, impurity removal can also be performed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0115] Alternatively, a process can be implemented whereby the resin composition filled in the bottle is degassed under reduced pressure after filtration using a filter.

[0116] [Substrate]

[0117] The type of substrate can be appropriately selected according to the application, but there are no particular limitations. 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 for plasma display panels (PDPs). In this invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred.

[0118] Furthermore, layers such as an adhesive layer and an oxide layer can be formed on the surface of these substrates.

[0119] Furthermore, as a substrate, a plate-shaped substrate (substrate) is used, for example.

[0120] Furthermore, the shape of the substrate is not particularly limited; it can be circular (circular plate) or rectangular (rectangular plate).

[0121] For the dimensions of the substrate, if it is circular, the diameter is, for example, 100–450 mm, preferably 200–450 mm. If it is rectangular, for example, the length of the shorter side is 100–1000 mm, preferably 200–700 mm.

[0122] Furthermore, when a photocurable film is formed on the surface of the resin layer or the metal layer, the resin layer or the metal layer becomes the substrate.

[0123] As a method for applying a photocurable resin composition to a substrate, coating is preferred.

[0124] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spraying, spin coating, slot coating, and inkjet coating. From the viewpoint of uniform thickness of the photocurable film, spin coating, slot coating, spraying, and inkjet coating are more preferred; from the viewpoint of easily obtaining the effects of the present invention, slot coating is preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a photocurable film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spraying, or inkjet coating are preferred; and for rectangular substrates, slot coating, spraying, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 2,000 rpm can be applied for approximately 10 seconds to 1 minute.

[0125] Furthermore, it is also possible to apply a method for transferring a coating film formed by applying it to a temporary support in advance using the above-described method onto a substrate.

[0126] Regarding the transfer method, in this invention, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used.

[0127] Furthermore, a process can also be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead removers (EBR) and air knives.

[0128] <Drying Process>

[0129] The pattern forming method of the present invention may include a step of drying the formed film (layer) to remove solvent after the film forming step (layer forming step) (drying step).

[0130] The preferred drying temperature is 50–150°C, more preferably 70–130°C, and even more preferably 90–110°C. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

[0131] <Developing Process>

[0132] The pattern forming method of the present invention includes a developing step of developing a developing pattern by developing the photocurable film after the first exposure step with a developing solution.

[0133] By developing, one of the exposed and unexposed areas is removed. The developing method is not particularly limited as long as it can form the desired pattern; examples include nozzle spraying, spraying, and immersion of the substrate in the developing solution. Nozzle spraying is preferred. The developing process can include steps such as continuously supplying developing solution to the substrate, holding the substrate in a substantially static state, vibrating the developing solution using ultrasonic waves, or a combination of these methods.

[0134] Development is performed using a developer. As a developer, if it is negative development, a developer that removes the unexposed parts (non-exposed areas) can be used, and if it is positive development, a developer that removes the exposed parts (exposed areas) can be used; there are no particular limitations.

[0135] In this invention, the use of an alkaline developer as a developer is referred to as alkaline development, and the use of a developer containing 50% by mass or more of an organic solvent as a developer is referred to as solvent development.

[0136] In alkaline development, the organic solvent content of the developer is preferably 10% by mass or less relative to the total mass of the developer, more preferably 5% by mass or less, even more preferably 1% by mass or less, and especially preferably a developer that does not contain organic solvents.

[0137] The developer used in alkaline development is preferably an aqueous solution with a pH of 10 to 15.

[0138] Examples of alkaline compounds included in the developing solution in alkaline 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 amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH), or tetraethylammonium hydroxide. Preferably, the alkaline compound is a metal-free compound, and more preferably, an ammonium compound.

[0139] For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass of the total amount of developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0140] There may be only one alkali compound or two or more alkali compounds. When there are two or more alkali compounds, it is preferable that their total number is within the above range.

[0141] In solvent development, the developer preferably contains more than 90% organic solvent. In this invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated by inputting the structural formula into ChemBioDraw (a chemical drawing software).

[0142] Regarding organic solvents, esters are preferably exemplified as follows: 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, and alkyl alkoxyacetic acids (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., such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) and alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc., such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, alkyl 2-alkoxypropionate, alkyl 2-eth ... Ethyl 2-alkoxy-2-methylpropionate, methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, etc. Cellulose-solerating agents include esters such as 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, and propylene glycol monopropyl ether acetate; ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons, such as toluene, xylene, anisole, and limonene; and sulfoxides, such as dimethyl sulfoxide.

[0143] In this invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is even more preferred.

[0144] The preferred development time is 10 seconds to 5 minutes. The temperature of the developing solution is not particularly limited and can generally be maintained between 20 and 40°C.

[0145] In the developing process, rinsing can be performed after treatment with developing solution.

[0146] In the case of solvent development, it is preferable to use an organic solvent different from the developer for rinsing.

[0147] In the case of alkaline development, it is preferable to rinse with pure water.

[0148] The preferred rinsing time is 5 seconds to 1 minute.

[0149] <Second Exposure Process>

[0150] The pattern forming method of the present invention includes a second exposure step of exposing the above-described developed pattern to obtain a pattern.

[0151] In the second exposure process, the photosensitive compound B is exposed to light to obtain a pattern.

[0152] For example, when photosensitive compound B is a photoalkali-generating agent described later, a pattern is obtained by cyclizing a specific resin.

[0153] For example, if the photosensitive compound B is a photopolymerization initiator or photoacid generator described later, and the specific resin contains a crosslinking group or the photocurable film contains a crosslinking agent or both, crosslinking is performed in the photocurable film to obtain a pattern.

[0154] The second exposure step may be exposure with light containing only the same wavelength as the light used in the first exposure step described above, preferably exposure with light containing a wavelength different from the light used in the first exposure step described above.

[0155] That is, in the second exposure process, photosensitive compound A may or may not be photosensitive.

[0156] For example, when the first exposure step is performed using i-rays (wavelength 365nm), the second exposure step can also be performed using i-rays. Examples of methods include using broadband light, i.e., a high-pressure mercury lamp (containing i-rays and other wavelengths of exposure light), for the second exposure step, or using h-rays (405nm) for the second exposure step.

[0157] When the photocurable film is a negative photocurable film, from the viewpoint of the chemical resistance of the obtained pattern, the exposure light in the second exposure step preferably includes light of the wavelength that exposes the photosensitive compound A, and more preferably light of a wavelength that includes light of the wavelength that exposes the photosensitive compound A and light of the wavelength that exposes the photosensitive compound B, but is different from the wavelength that exposes the photosensitive compound A.

[0158] For example, photosensitive compound A is a photoradical polymerization initiator, and photosensitive compound B is a photoalkali-generating agent. In the second exposure step, when photosensitive compound A is also exposed to light in addition to photosensitive compound B, not only cyclization but also free radical polymerization will proceed further. Therefore, it is believed that the chemical resistance of the obtained pattern is further improved.

[0159] As mentioned above, the exposure light in the second exposure process also includes light of the wavelength sensitive to photosensitive compound A, which can sometimes produce patterns with excellent film strength and solvent resistance.

[0160] Furthermore, as one of the preferred methods, for example, the following method can be used: if the photocurable film contains a crosslinking agent and the crosslinking agent is crosslinked in the first exposure step, the crosslinking agent is not completely crosslinked in the first exposure step, and after development, the crosslinking agent is crosslinked in the second exposure step by using exposure light containing light of a wavelength that is also used to sensitize the photosensitive compound A.

[0161] The wavelength of light containing the photosensitive compound B in the exposure light of the second exposure step can be appropriately set taking into account the sensitivity of the photosensitive compound B described later. It is preferably 190 to 1,000 nm, more preferably 200 to 550 nm, and even more preferably 200 to 450 nm.

[0162] If the exposure wavelength is referred to as the relationship with the light source, examples include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband light (light containing at least two wavelengths selected from gamma, h, i-rays and light with wavelengths shorter than i-rays. For example, high-pressure mercury lamps without filters can be cited), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beams, etc.

[0163] Among these, the light source in the first exposure step is preferably i-rays, h-rays, or broadband light. This results in particularly high exposure sensitivity.

[0164] Filters that remove specific wavelengths can be used in these light sources, but for example, in order to promote the photosensitivity of photosensitive compound A in the second exposure step, it is particularly preferable not to use filters or the like, but to use a light source that contains light of various wavelengths in the range of 200 to 600 nm, such as the high-pressure mercury lamp mentioned above.

[0165] In the second exposure step, at least a portion of the developed pattern obtained in the developing step needs to be exposed, but preferably all of the pattern is exposed.

[0166] The exposure amount in the second exposure step is calculated based on the exposure energy at the wavelength where the photosensitive compound B is sensitive, and is preferably 100–20,000 mJ / cm². 2More preferably, it is 200–15,000 mJ / cm². 2 .

[0167] From the viewpoint of shrinkage of the obtained pattern, the temperature in the second exposure process is preferably 20 to 300°C, more preferably 50 to 200°C, and even more preferably 50 to 150°C.

[0168] Here, the temperature in the second exposure process refers to the set temperature in the exposure apparatus that performs the second exposure process, which can be set, for example, by using an exposure apparatus with temperature adjustment function to perform the second exposure process.

[0169] The exposure section of the photocurable film becomes hot due to exposure. Therefore, it is believed that by setting the set temperature in the exposure apparatus within the aforementioned range, exposure can be performed while cooling the photocurable film, thereby suppressing pattern shrinkage.

[0170] The thickness of the pattern obtained through the second exposure process can be set to, for example, 0.5 μm or more, or 1 μm or more. Furthermore, as an upper limit, it can be set to 100 μm or less, or 40 μm or less.

[0171] <Heating Process>

[0172] The pattern forming method of the present invention may further include a heating step for heating the pattern after the second exposure step.

[0173] During the heating process, a cyclization reaction of a specific resin is carried out.

[0174] Furthermore, sometimes time-curable films contain crosslinking agents other than specific resins, but also crosslink unreacted crosslinking groups in the compounds of these crosslinking agents.

[0175] The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 140 to 400°C, and even more preferably 160 to 350°C.

[0176] The heating rate from the initial temperature to the maximum heating temperature during the heating process is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. Setting the heating rate to 1°C / minute or more ensures productivity, while setting it to 12°C / minute or less alleviates residual stress in the pattern.

[0177] The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and especially preferably 30 to 240 minutes.

[0178] In particular, when forming a multilayer laminate, from the viewpoint of ensuring the tightness of the interlayer adhesion of the pattern, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is uncertain, but it is believed that by setting the temperature within the above range, the crosslinking groups in the specific resins or crosslinking agents between the layers can undergo crosslinking reactions with each other.

[0179] Heating can be performed in stages. For example, a pretreatment step can be performed where the temperature is increased from 25°C to 180°C at a rate of 3°C / min and held at 180°C for 60 minutes, and then increased from 180°C to 200°C at a rate of 2°C / min and held at 200°C for 120 minutes. The heating temperature for this pretreatment step is preferably 100–200°C, more preferably 110–190°C, and even more preferably 120–185°C. In this pretreatment step, as described in U.S. Patent No. 9,159,547, it is also preferable to perform the treatment simultaneously with ultraviolet irradiation. These pretreatment steps can improve the properties of the membrane. The pretreatment step can be performed in a short time, approximately 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a two-stage or more step; for example, a first pretreatment step can be performed in the range of 100–150°C, followed by a second pretreatment step in the range of 150–200°C.

[0180] Furthermore, cooling can be performed after heating, and the preferred cooling rate in this case is 1 to 5°C / minute.

[0181] In order to prevent the decomposition of polymer precursors, it is preferable to perform the heating process in an atmosphere with a low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0182] There are no particular limitations on the heating mechanism used in the heating process; examples include heating plates, infrared thermometers, electric ovens, and hot air ovens.

[0183] From the viewpoint of pattern shrinkage, the pattern forming method of the present invention can also be configured to exclude the process of heating the developed pattern obtained by the developing process (heating process) after the developing process and before the second exposure process.

[0184] In particular, when the photosensitive compound B is a photoalkali-generating agent, from the viewpoint of pattern shrinkage, it is preferable not to include a process of heating the pattern at 200°C or above before the second exposure process, and more preferably not to include a process of heating the pattern at 160°C or above.

[0185] <Metal Layer Formation Process>

[0186] The pattern forming method of the present invention preferably includes a metal layer forming step that forms a metal layer on the surface of the pattern after the second exposure step (or after the heating step if a heating step is included).

[0187] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0188] There are no particular limitations on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be used. For example, methods such as photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited.

[0189] The thickness of the metal layer, in the thickest part, is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

[0190] <Uses>

[0191] Examples of fields in which patterns obtained by the pattern forming method of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress-relief films. Other examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or patterns formed by etching insulating films used in practical mounting applications as described above. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimides,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0192] Furthermore, the patterns obtained by the pattern forming method of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, in the application of etched forming parts, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0193] (Manufacturing method of laminated bodies)

[0194] The method for manufacturing the laminate of the present invention preferably includes the pattern forming method of the present invention.

[0195] The laminate obtained by the manufacturing method of the present invention is a laminate containing two or more patterns, or it can be a laminate with three to seven layers.

[0196] In the above-mentioned laminate, at least one of the patterns in the two or more layers is a pattern obtained by the pattern forming method of the present invention. From the viewpoint of suppressing pattern shrinkage or deformation of the pattern accompanying the shrinkage, all the patterns included in the above-mentioned laminate are preferably patterns obtained by the pattern forming method of the present invention.

[0197] Regarding the aforementioned laminate, it is preferable to include two or more patterns, with a metal layer between any of the patterns. The metal layer is preferably formed by the aforementioned metal layer forming process.

[0198] As an example of the aforementioned laminate, a laminate containing at least three layers in which a first pattern, a metal layer, and a second pattern are stacked sequentially is preferred.

[0199] Both the first pattern and the second pattern described above are preferably patterns obtained by the pattern forming method of the present invention. The photocurable resin composition of the present invention used to form the first pattern and the photocurable resin composition of the present invention used to form the second pattern may be of the same composition or of different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0200] <Layering Process>

[0201] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0202] The lamination process includes a series of steps, namely (a) a film formation step (layer formation step), (b) a first exposure step, (c) a development step, and (d) a second exposure step, performed sequentially on the surface of the pattern (resin layer) or metal layer. However, it may be possible to repeat only the film formation step (a). Furthermore, at least one of a heating step and (e) a metal layer formation step may be included after the second exposure step (d). The heating step may be performed after steps (a) to (d) and (e) may be repeated multiple times as needed. It is beyond doubt that the lamination process may appropriately include the aforementioned drying step, etc.

[0203] When performing a further lamination process after the lamination process, a surface activation treatment process may be performed after the first exposure process, after the second exposure process, or after the metal layer formation process. Plasma treatment can be exemplified as a surface activation treatment.

[0204] In cases where the durability of the laminate is of priority, the manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the metal layer and the resin composition layer.

[0205] The surface activation treatment process is usually performed after the metal layer formation process, but the metal layer formation process can be performed after the surface activation treatment process of the resin composition layer after the development process described above.

[0206] Surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the area of ​​the metal layer where the resin composition layer is formed on the surface. As described above, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved.

[0207] Furthermore, surface activation treatment is preferably performed on part or all of the exposed resin composition layer (resin layer). As described above, by performing surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. In particular, in cases such as negative development or curing of the resin composition layer, it is less likely to be damaged by surface treatment, and adhesion is easily improved.

[0208] As a surface activation treatment, specifically, methods can be selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixtures, argon / oxygen mixtures, etc.), plasma treatment, corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, surface treatment based on ultraviolet (UV) ozone method, treatment after immersion in hydrochloric acid aqueous solution to remove oxide coating and then immersion in an organic surface treatment agent containing at least one of amino and thiol groups, 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, it is 1000 to 100,000 J / m 2 The optimal value is 10,000 to 50,000 J / m 2 .

[0209] The above-mentioned layering process is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

[0210] For example, a structure with 3 or more but less than 7 resin layers is preferred, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer. More preferably, a structure with 3 or more but less than 5 resin layers is preferred.

[0211] The composition, shape, and film thickness of each of the above layers can be the same or different.

[0212] In this invention, especially after the metal layer is formed, it is further preferred that the pattern (resin layer) of the photocurable resin composition is formed by covering the metal layer. Specifically, an example is to repeat the sequence of (a) film formation step, (b) first exposure step, (c) development step, (d) second exposure step, and (e) metal layer formation step. By alternating the above-mentioned steps (a) to (d) for forming the pattern and the metal layer formation step, the pattern and the metal layer can be stacked alternately.

[0213] (Manufacturing methods for electronic devices)

[0214] The present invention also discloses a method for manufacturing an electronic device including the pattern forming method of the present invention or the method for manufacturing a laminate of the present invention. Specific examples of electronic devices in which the photocurable resin composition of the present invention is used in the formation of an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and in Figure 1, and these contents are incorporated herein by reference.

[0215] The following describes in detail the photocurable resin composition used in the pattern forming method, the laminate manufacturing method, or the electronic device manufacturing method of the present invention.

[0216] (Photocurable resin composition)

[0217] The first embodiment of the photocurable resin composition of the present invention is the photocurable resin composition used in the pattern forming method of the present invention, the laminate manufacturing method of the present invention, or the electronic device manufacturing method of the present invention. Specifically, the first embodiment of the photocurable resin composition of the present invention comprises at least one resin selected from polyimide precursors and polybenzoxazole precursors, a photosensitive compound A sensitive to the exposure wavelength in the first exposure step, and a photosensitive compound B sensitive to the exposure wavelength in the second exposure step. The photosensitive compound A is a compound that causes a change in the solubility of the photocurable film relative to the developer in the first exposure step. At least one of the photosensitive compounds A and B is a photoalkali-generating agent.

[0218] Furthermore, the second embodiment of the photocurable resin composition of the present invention comprises at least one resin selected from polyimide precursor and polybenzoxazole precursor, photosensitive compound A and photosensitive compound B, wherein photosensitive compound A is a compound capable of changing the solubility of the resin by photosensitization, at least one of photosensitive compound A and photosensitive compound B is a photoalkali-generating agent, and the difference between the maximum absorption wavelength of photosensitive compound A and the maximum absorption wavelength of photosensitive compound B is 100 nm or more.

[0219] According to the photocurable resin composition of the second method described above, it is believed that when the photocurable film formed from the above composition is used in a pattern forming method including the first exposure step, the development step and the second exposure step described above, shrinkage of the obtained pattern relative to the developed pattern after development can be suppressed.

[0220] Except for the limitation that the difference between the maximum absorption wavelength of photosensitive compound A and the maximum absorption wavelength of photosensitive compound B is 100 nm or more in the second embodiment, the components contained in the photocurable resin composition of the first embodiment are the same as the components contained in the photocurable resin composition of the second embodiment.

[0221] In this invention, the photosensitive compound A is preferably a compound that generates free radicals through the first exposure step described above, and more preferably a photoradical polymerization initiator.

[0222] According to the above method, in the first exposure step, free radical polymerization is promoted in the photocurable film to enable development.

[0223] In this invention, the photosensitive compound A is preferably a compound that generates acid through the first exposure step described above, and more preferably a photoacid generator.

[0224] According to the above method, in the first exposure step, acid-based crosslinking is promoted in the photocurable film or acid is generated in the photocurable film to increase the solubility in the alkaline developer, thereby enabling development.

[0225] In this invention, the photosensitive compound B is preferably a compound that generates alkali through the second exposure step described above, and more preferably a photoalkali-generating agent.

[0226] According to the above method, in the second exposure step, cyclization of a specific resin is promoted in the developed pattern, thereby obtaining the pattern.

[0227] The combination of photosensitive compound A and photosensitive compound B in the photocurable resin composition of the present invention is preferably any one of the following methods 1 to 5.

[0228] Method 1: Photosensitive compound A is a photopolymerization initiator, and photosensitive compound B is a photoalkali-producing agent.

[0229] Method 2: Photosensitive compound A is a photoacid generator, and photosensitive compound B is a photoalkali generator.

[0230] Method 3: Photosensitive compound A is a photoalkali-generating agent, and photosensitive compound B is a photopolymerization initiator.

[0231] Method 4: Photosensitive compound A is a photoalkali-producing agent, and photosensitive compound B is a photoacid-producing agent.

[0232] Method 5: Both photosensitive compound A and photosensitive compound B are photoalkalizing agents.

[0233] According to method 1, method 3 or method 4 above, a negative photocurable film can be obtained.

[0234] In methods 2 and 5 above, negative or positive photocurable films can be obtained.

[0235] Of these, from the viewpoint of pattern resolution, any one of methods 1 to 4 is preferred.

[0236] From the viewpoint of improving the chemical resistance of the pattern, method 1 or method 2 is preferred.

[0237] From the viewpoint of obtaining a positively photocurable film, method 2 is preferred.

[0238] <Method 1>

[0239] In Method 1, the photocurable resin composition preferably further comprises a free radical crosslinking agent, which will be described later.

[0240] For example, in the pattern forming method of the present invention, when using the photocurable resin composition of method 1, crosslinking of the crosslinking agent is promoted in the exposure section of the first exposure step, and cyclization of a specific resin is promoted in the exposure section of the second exposure step.

[0241] <Method 2>

[0242] In Method 2, when a negative photocurable film is formed, the photocurable resin composition preferably further includes other crosslinking agents described later.

[0243] For example, in the pattern forming method of the present invention, when a negative photocurable film is formed using the photocurable resin composition of method 2, crosslinking of the crosslinking agent is promoted in the exposure section of the first exposure step, and cyclization of a specific resin is promoted in the exposure section of the second exposure step.

[0244] In Method 2, when forming a positive photocurable film, the photocurable resin composition may also contain other crosslinking agents as described later, or may not contain crosslinking agents.

[0245] For example, in the pattern forming method of the present invention, when a positive photocurable film is formed using the photocurable resin composition of method 2, acid is generated in the exposure section of the first exposure step, increasing the solubility of the film relative to the developer such as the alkaline developer, and promoting the cyclization of a specific resin in the exposure section of the second exposure step.

[0246] <Method 3>

[0247] In Method 3, the photocurable resin composition preferably further comprises a free radical crosslinking agent, which will be described later.

[0248] For example, in the pattern forming method of the present invention, when using the photocurable resin composition of method 3, cyclization of a specific resin is promoted in the exposure section of the first exposure step, and crosslinking of the crosslinking agent is promoted in the exposure section of the second exposure step.

[0249] <Method 4>

[0250] In Method 4, the photocurable resin composition preferably further comprises other crosslinking agents described later.

[0251] For example, in the pattern forming method of the present invention, when using the photocurable resin composition of method 4, cyclization of a specific resin is promoted in the exposure section of the first exposure step, and crosslinking of the crosslinking agent is promoted in the exposure section of the second exposure step.

[0252] <Method 5>

[0253] In Method 5, the photocurable resin composition preferably further comprises other crosslinking agents described later.

[0254] For example, in the pattern forming method of the present invention, when using the photocurable resin composition of method 5, at least one of cyclization of a specific resin and crosslinking of a crosslinking agent is promoted in the exposure section of the first exposure step, and at least one of cyclization of a specific resin and crosslinking of a crosslinking agent is promoted in the exposure section of the second exposure step.

[0255] The following describes in detail the components contained in the photocurable resin composition of the present invention.

[0256] <Specific Resins>

[0257] The photocurable resin composition of the present invention comprises at least one resin (specific resin) selected from polyimide precursors and polybenzoxazole precursors.

[0258] The photocurable resin composition of the present invention preferably contains a polyimide precursor as a specific resin.

[0259] Certain resins may also possess crosslinking groups. Examples of crosslinking groups, such as R described later, can be found in other resins. 113 and R114 The cross-linking groups are cited in the description.

[0260] [Polyimide precursor]

[0261] From the viewpoint of the film strength of the obtained pattern, the polyimide precursor preferably has repeating units represented by the following formula (1).

[0262] [Chemical Formula 1]

[0263]

[0264] In equation (1), A 1 and A 2 Each independently represents an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0265] -A 1 and A 2 -

[0266] A in equation (1) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, preferably an oxygen atom.

[0267] -R 111 -

[0268] R in equation (1) 111 This refers to a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups composed of two or more of these. Preferably, it is a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or groups composed of two or more of these. More preferably, it is an aromatic group with 6 to 20 carbon atoms.

[0269] R in equation (1) 111 Preferably, it is derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0270] Specifically, the diamine is preferably a diamine comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of two or more of these groups, and more preferably a diamine comprising an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following aromatic groups. In the following formulas, * independently denotes bonding sites with other structures.

[0271] [Chemical Formula 2]

[0272]

[0273] In the formula, A is preferably a single bond or a group consisting of an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a combination of two or more of these groups. More preferably, it is a group selected from the group consisting of a single bond, including an alkylene group with 1 to 3 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, -S-, and S(=O)2-. More preferably, it is a divalent group selected from -CH2-, -O-, -S-, -S(=O)2-, -C(CF3)2-, and -C(CH3)2-.

[0274] As a diamine, specifically, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminoaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(methyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-Diaminobiphenyl, 4,4'-Diaminodiphenyl ether, 3,3-Diaminodiphenyl ether, 4,4'-Diaminodiphenylmethane or 3,3'-Diaminodiphenylmethane, 4,4'-Diaminodiphenyl sulfone or 3,3'-Diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl sulfone or 3,3'-Diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl ketone or 3,3'-Diaminodiphenyl ketone, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 2,2'-Dimethyl-4,4'-Diaminobiphenyl (4,4'-Diamino-2,2'-Dimethylbiphenyl), 3,3'-Dimethoxy-4,4'-Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane 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'-diamino-p-terphenyl, 4,4'-bis(4-phenoxy)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'-Diaminodiphenyl sulfone, 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-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3 1,2-Aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)benzene] [4,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4, At least one diamine selected from the following: 4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0275] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0276] Furthermore, the diamine having two or more alkylene glycol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0277] From the perspective of the softness of the obtained pattern, R in equation (1) 111 Preferred from -Ar 0 -L 0 -Ar 0 - indicates. Ar 0Each group is independently an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, especially preferably 6 to 10), and is preferably phenylene. 0 This refers to a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by fluorine atoms, or a group consisting of -O-, -C(=O)-, -S-, -S(=O)2-, -NHCO-, or a combination of two or more of these. 0 The meaning of the preferred range is the same as the meaning of A above.

[0278] From the perspective of i-ray transmittance, R in equation (1) 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0279] [Chemical Formula 3]

[0280]

[0281] In equation (51), R 50 ~R 57 R is an organic group that is independently composed of a hydrogen atom, a fluorine atom, or a monovalent organic group. 50 ~R 57 At least one of them is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group, and * represents the bonding site with other structures independently.

[0282] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0283] [Chemical Formula 4]

[0284]

[0285] In equation (61), R 58 and R 59 Each can be independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

[0286] Examples of diamine compounds endowed with the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One of these compounds may be used, or a combination of two or more may be used.

[0287] -R115 -

[0288] R in equation (1) 115 The term represents a tetravalent organic group. Preferably, the tetravalent organic group is a tetravalent organic group containing an aromatic ring, and more preferably, it is a group represented by the following formula (5) or formula (6).

[0289] [Chemical Formula 5]

[0290]

[0291] R 112 The meaning of is the same as that of A, and the preferred range is also the same. *Indicates the bonding site with other structures independently.

[0292] R in equation (1) 115 Specifically, the tetravalent organic group can be exemplified by the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[0293] [Chemical Formula 6]

[0294]

[0295] R 115 R represents a tetravalent organic group. 115 The meaning of R in equation (1) 115 The meanings are the same.

[0296] Specific examples of tetracarboxylic dianhydrides include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (4,4'-diphthalic anhydride), 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone 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-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxylic acid). 2,2-Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-Bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4, At least one of the following: 5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl derivatives thereof having 1 to 6 carbon atoms, and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0297] Furthermore, as a preferred example, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be cited.

[0298] R is also preferred 111 and R 115 At least one of them has an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0299] -R 113 and R 114 -

[0300] R in equation (1) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. R is preferred. 113 and R 114At least one of them contains a crosslinking group, and more preferably both contain crosslinking groups. As a crosslinking group, it is preferably a group capable of crosslinking through the action of free radicals, acids, bases, etc. Examples include groups with vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acylmethyl, epoxy, oxacyclobutyl and other cyclic ether groups, benzoxazolyl, block isocyanate, hydroxymethyl, and amino groups, preferably groups with vinyl unsaturated bonds, cyclic ether groups, alkoxymethyl or hydroxymethyl groups. The aforementioned groups with vinyl unsaturated bonds are preferably groups with free radical polymerization properties.

[0301] Examples of groups having vinyl unsaturated bonds include vinyl, allyl, vinylphenyl and other substituted vinyl groups that are directly bonded to the aromatic ring, (meth)acryloyl, and groups represented by the following formula (III).

[0302] [Chemical Formula 7]

[0303]

[0304] In equation (III), R 200 It represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0305] In addition, methyl is preferred when drug resistance is a priority.

[0306] In equation (III), * indicates the bonding site with other structures.

[0307] In equation (III), R 201 It represents alkylene groups with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or polyalkoxide groups.

[0308] Preferred R 201 Examples include ethylene, propyleneene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH2CH(OH)CH2-, and polyalkoxide, more preferably ethylene, propyleneene, trimethylene, -CH2CH(OH)CH2-, and polyalkoxide. From the viewpoint that formula (1) or formula (2) is easily satisfied in organic membranes, polyalkoxide is even more preferred.

[0309] In this invention, polyalkoxide refers to an alkoxide group directly bonded to two or more groups. The alkylene groups of the multiple alkoxide groups contained in the polyalkoxide group may be the same or different.

[0310] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0311] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0312] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0313] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0314] From the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethoxy, or a group consisting of multiple ethoxy groups bonded to multiple propoxy groups are preferred as polyethoxy groups. Polyethoxy or polypropoxy groups are more preferred, and polyethoxy is even more preferred. In the aforementioned groups consisting of multiple ethoxy groups bonded to multiple propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred manner for the number of repetitions of the ethoxy groups, etc., in these groups is as described above.

[0315] R 113 or R 114 The atom is hydrogen, benzyl, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl, but more preferably from the viewpoint of solubility relative to aqueous developer.

[0316] From the perspective of solubility in organic solvents, R 113 or R 114 Preferably, it is a monovalent organic group. As a monovalent organic group, it is preferably a straight-chain or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group that can be substituted by an aromatic group.

[0317] The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic alkyl group). The alkyl group can be straight-chain, branched, or cyclic. Examples of straight-chain 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, and 2-ethylhexyl. Cyclic alkyl groups can be monocyclic or polycyclic. Examples of monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alkyl groups include adamantyl, norbornyl, borneol, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, dicyclohexyl, and pinenyl. Furthermore, the alkyl group that can be substituted with an aromatic group is preferably a straight-chain alkyl group that can be substituted with an aromatic group, as described below.

[0318] As an aromatic group, specifically, substituted or unsubstituted aromatic hydrocarbon groups (as cyclic structures constituting the group, examples include benzene rings, naphthyl rings, biphenyl rings, fluorene rings, cyclopentadiene rings, indene rings, azulene rings, heptadene rings, indene rings, perylene rings, pentabenzene rings, acenaphthene rings, phenanthrene rings, anthracene rings, and tetrabenzene rings, etc.). (chrysene) ring, triphenylene ring, etc.) or substituted or unsubstituted aromatic heterocyclic groups (as constituting groups, fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthrene-rhein ring, thiophene ring, benzopyran ring, xanthan ring, phenoxthia ring, phenothiazine ring, or phenothiazine ring).

[0319] Furthermore, the polyimide precursor preferably has fluorine atoms in the repeating units. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, and it is actually 50% by mass or less.

[0320] Furthermore, to improve adhesion to the substrate, an aliphatic group with a siloxane structure can be copolymerized with a repeating unit represented by formula (1). Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0321] The repeating unit represented by equation (1) is preferably the repeating unit represented by equation (1-A) or equation (1-B).

[0322] [Chemical Formula 8]

[0323]

[0324] A 11 and A 12 Represents oxygen atom or -NH-, R 111 and R 112 Each of the following independently represents a divalent organic group, R 113 and R 114 Each organic group, representing a hydrogen atom or a monovalent organic group, is more preferably R. 113 and R 114 At least one of them is a cross-linking group.

[0325] A 11 A 12 R 111 R 113 and R 114 The meaning of the preferred range is respectively the same as A in equation (1). 1 A 2 R 111 R 113 and R 114 The meaning of the preferred range is the same.

[0326] R 112 The meaning of the preferred range is the same as R in equation (5). 112 The meanings are the same, with oxygen atoms being more preferred.

[0327] In formula (1-A), the carbonyl group is preferably bonded to positions 4, 5, 3', or 4' on the benzene ring. In formula (1-B), the preferred positions are 1, 2, 4, or 5.

[0328] In the polyimide precursor, the repeating unit represented by formula (1) can be one type or two or more types. Furthermore, it may also contain structural isomers of the repeating unit represented by formula (1). In addition to the repeating unit of formula (1) mentioned above, the polyimide precursor may also contain other types of repeating units.

[0329] As one embodiment of the polyimide precursor in this invention, it can be exemplified that 50 mol% or more, further 70 mol% or more, and especially 90 mol% or more of the total repeating units are polyimide precursors of repeating units represented by formula (1). As an upper limit, it is actually 100 mol% or less.

[0330] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0331] The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0332] In this specification, the dispersion of molecular weight refers to the value of weight-average molecular weight divided by number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0333] Furthermore, when the resin composition comprises multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when considering the multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0334] Polyimide precursors are obtained by reacting dicarboxylic acids or dicarboxylic acid derivatives with diamines. For example, they can be obtained by halogenating dicarboxylic acids or dicarboxylic acid derivatives with a halogenating agent followed by reaction with a diamine.

[0335] More specifically, the following methods can be used to obtain polyamic acid: reacting tetracarboxylic dianhydride and diamine at low temperature; reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid and then esterifying it using a condensing agent or an alkylating agent; obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting it with diamine in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride and alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. Of the above manufacturing methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred.

[0336] Examples of condensing agents include dicyclohexyl carbodiimide, diisopropyl carbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroxyquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0337] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0338] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

[0339] Furthermore, when manufacturing polyimide precursors, it is preferable to use non-halogen catalysts for synthesis. As such non-halogen catalysts, known amidation catalysts that do not contain halogen atoms can be used without particular limitation, such as boron oxide trimers, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds. Examples of such carbodiimide compounds include N,N'-diisopropyl carbodiimide and N,N'-dicyclohexyl carbodiimide.

[0340] In the method for manufacturing polyimide precursors, an organic solvent is preferably used during the reaction. The organic solvent can be one type or two or more types.

[0341] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

[0342] Other examples include ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

[0343] In methods for manufacturing polyimide precursors, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.

[0344] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diacerbicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0345] When manufacturing polyimide precursors, a step of precipitating solids is preferably included. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby enabling solid precipitation.

[0346] More specifically, after filtering the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is placed in a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof to precipitate the polymer component as a solid. After drying, a polyimide precursor can be obtained. To improve purification, the polyimide precursor can be repeatedly subjected to operations such as redissolving, redepositing, and drying. Additionally, a step of removing ionic impurities using an ion exchange resin may also be included.

[0347] -End- Capping Agent-

[0348] When manufacturing polyimide precursors, etc., to further improve storage stability, it is preferable to seal residual carboxylic anhydrides, anhydride derivatives, or amino groups at the resin end of the polyimide precursor, etc. When sealing residual carboxylic anhydrides and anhydride derivatives at the resin end, end-capping agents include monools, phenols, thiols, benzenethiophenols, monoamines, etc. Considering reactivity and film stability, monools, phenols, or monoamines are more preferred. Preferred monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butyl alcohol, adamantanol, etc. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds for 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, and 1-carboxy-5-aminonaphthalene. 2-Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0349] Furthermore, when sealing the amino group at the end of the resin, a compound having a functional group capable of reacting with the amino group can be used for sealing. Preferred end-capping agents for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Examples of preferred carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Examples of preferred carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pentavalloyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0350] [Polybenzoxazole precursor]

[0351] The polybenzoxazole precursor preferably contains repeating units represented by the following formula (2).

[0352] [Chemical Formula 9]

[0353]

[0354] In equation (2), R 121 R represents a divalent organic group. 122 R represents a tetravalent organic group. 123 and R 124 Each can be used to independently represent a hydrogen atom or a monovalent organic group.

[0355] -R 121 -

[0356] In equation (2), R 121 This indicates a divalent organic group. The divalent organic group is preferably a group comprising at least one of an aliphatic group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, especially preferably 1 to 6) and an aromatic group (preferably with 6 to 22 carbon atoms, more preferably 6 to 14, especially preferably 6 to 12). As a constituent of R... 121 Aromatic groups, such as R in equation (1) above, can be cited as examples. 111 Examples. As the aforementioned aliphatic group, a straight-chain aliphatic group is preferred. R 121 Preferably derived from 4,4'-oxybenzoyl chloride.

[0357] -R 122 -

[0358] In equation (2), R 122 This indicates a tetravalent organic group. As a tetravalent organic group, its meaning is the same as R in formula (1) above. 115 The meanings are the same, and the preferred ranges are also the same. R 122 Preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0359] -R 123 and R 124 -

[0360] R 123 and R 124 Each of the above formulas independently represents a hydrogen atom or a monovalent organic group, with the same meaning as R in formula (1) above. 113 and R 114 The meanings are the same, and the preferred ranges are also the same.

[0361] In addition to the repeating unit in formula (2) above, polybenzoxazole precursors may also contain other types of repeating units.

[0362] From the viewpoint of being able to suppress the warping of the pattern accompanying the ring closure, the polybenzoxazole precursor preferably also contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0363] [Chemical Formula 10]

[0364]

[0365] Z has both structure a and structure b, R 1s R is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms). 2s R is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms). 3s R 4s R 5s R 6s At least one of the components is an aromatic group (preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms, especially preferably 6-10 carbon atoms), and the remainder is a hydrogen atom or an organic group with 1-30 carbon atoms (preferably 1-18 carbon atoms, more preferably 1-12 carbon atoms, especially preferably 1-6 carbon atoms), which may be the same or different. The polymerization of structure a and structure b can be block polymerization or random polymerization. In part Z, it is preferred that structure a is 5-95 mol%, structure b is 95-5 mol%, and a+b is 100 mol%.

[0366] In equation (SL), as a preferred Z, R in structure b can be cited as an example. 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. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the above molecular weight within the above range, the elastic modulus of the dehydrated and ring-closed polybenzoxazole precursor is reduced, and it can simultaneously achieve the effects of suppressing warpage and improving solubility.

[0367] When the polybenzoxazole precursor contains a diamine residue represented by formula (SL) as another type of repeating unit, it is preferable, from the viewpoint of improving the alkali solubility of the photocurable resin composition, that the repeating unit also contains a tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the tetracarboxylic acid dianhydride. Examples of such tetracarboxylic acid residues include R in formula (1). 115 Examples.

[0368] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

[0369] The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0370] -Acid Value-

[0371] From the viewpoint of the strength of the obtained patterned film, the acid value of the specific resin is preferably 80 mg KOH / g or less, more preferably 50 mg KOH / g or less, even more preferably 30 mg KOH / g or less, and particularly preferably 20 mg KOH / g or less. Furthermore, the lower limit of the above-mentioned acid value is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, and even more preferably 10 mg KOH / g or more.

[0372] It is believed that if the acid value is within the above range, it can inhibit the neutralization of specific compounds through acid groups, thereby easily promoting the cyclization of specific resins.

[0373] The acid value mentioned above is determined by a known method, for example, by the method described in JIS K 0070:1992.

[0374] The content of the specific resin in the photocurable resin composition of the present invention, relative to the total solids content of the photocurable resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, even more preferably 60% by mass or more, and still more preferably 70% by mass or more. Furthermore, the content of the specific resin in the photocurable resin composition of the present invention, relative to the total solids content of the photocurable resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still more preferably 95% by mass or less.

[0375] The photocurable resin composition of the present invention may contain only one specific resin or may contain two or more resins. When containing two or more resins, the total amount is preferably within the above-mentioned range.

[0376] <Other Resins>

[0377] The photocurable resin composition of the present invention may also contain other resins (hereinafter also simply referred to as "other resins") that are different from the specific resin.

[0378] Other examples of resins include polyamide-imide, polyamide-imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, and acrylic resins.

[0379] Other examples of resins include (meth)acrylamide resin, urethane resin, butyral resin, styrene resin, polyether resin, and polyester resin.

[0380] For example, by further adding acrylic resin, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can be obtained.

[0381] For example, by replacing the polymerizable compounds described later or by adding an acrylic resin with a high polymerizable group value of less than 20,000 weight average molecular weight to the composition, the coatability of the composition and the solvent resistance of the organic film can be improved.

[0382] When the photocurable resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the composition 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.

[0383] Furthermore, the content of other resins in the photocurable resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the composition.

[0384] Furthermore, as a preferred embodiment of the photocurable resin composition of the present invention, it is also possible to use a composition with a low content of other resins. In the above embodiment, the content of other resins relative to the total solids content of the composition 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. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0385] The photocurable resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, the total amount is preferably within the above-mentioned range.

[0386] <Photosensitive compound A>

[0387] The photocurable resin composition of the present invention comprises a photosensitive compound A that is sensitive to the exposure wavelength in the first exposure step described above.

[0388] Whether a photosensitive compound is sensitive to the exposure wavelength in the first exposure step can be determined by the following method.

[0389] A composition for forming a mold film is prepared by dissolving a photosensitive compound and polymethyl methacrylate (PMMA) in methyl ethyl ketone. The content of the photosensitive compound in the composition for forming the mold film, relative to the total mass of photosensitive compound A and PMMA, is set to 0.5 mmol / g. Furthermore, the amount of methyl ethyl ketone used in the composition for forming the mold film, relative to the total mass of photosensitive compound A and PMMA, can be appropriately set according to the film thickness of the mold film, as described later.

[0390] When the photocurable resin composition contains the sensitizer described later, the sensitizer is also added to the mold film in such a way that the mass ratio of the photosensitive compound to the sensitizer in the photocurable resin composition is the same as the mass ratio of the photosensitive compound to the sensitizer in the mold film.

[0391] Furthermore, the weight-average molecular weight of PMMA was set to 10,000.

[0392] The obtained mold film forming composition is then coated onto glass and heat-dried at 80°C for 1 minute to obtain the mold film. The thickness of the mold film is then 10 μm. Next, the composition film is exposed using the same light source as in the first exposure step, with the same wavelength and irradiation intensity as the previous exposure.

[0393] Following the above exposure, the mold film and the glass on which the mold film is formed were immersed in a methanol / THF = 50 / 50 (mass ratio) solution for 10 minutes while being subjected to ultrasonic waves. The extract extracted into the above solution was analyzed by HPLC (high performance liquid chromatography), and the residual rate of the photosensitive compound was calculated using the following formula.

[0394] Residual rate of photosensitive compound (%) = Amount of photosensitive compound in the mold film after exposure (mol) / Content of photosensitive compound in the mold film before exposure (mol) × 100

[0395] Furthermore, when the residual rate of the aforementioned photosensitive compound is less than 80%, the photosensitive compound is determined to be a compound sensitive to the exposure wavelength in the first exposure step. The residual rate is preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less. The lower limit of the residual rate is not particularly limited and can be 0%.

[0396] When the residual rate of the aforementioned photosensitive compound is 80% or more, the photosensitive compound is determined to be a compound that is not sensitive to the exposure wavelength in the first exposure step. The residual rate is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. There is no particular upper limit to the residual rate, and it can be 100%.

[0397] The photosensitive compound A may or may not be sensitive to the exposure wavelength in the second exposure step. From the viewpoint of the film strength and solvent resistance of the obtained pattern, it is preferable to be sensitive to the exposure wavelength in the second exposure step.

[0398] Regarding whether there is sensitivity to the exposure wavelength in the second exposure step, in the method for determining whether there is sensitivity to the exposure wavelength in the first exposure step, it can be determined by replacing the description of "first exposure step" with the description of "second exposure step".

[0399] In a second embodiment of the photocurable resin composition of the present invention, the difference between the maximum absorption wavelength of photosensitive compound A and the maximum absorption wavelength of photosensitive compound B is 100 nm or more, preferably 100 to 300 nm, and more preferably 100 to 200 nm.

[0400] The maximum absorption wavelength of photosensitive compound A is preferably 190–450 nm, more preferably 200–450 nm.

[0401] Furthermore, the maximum absorption wavelength of photosensitive compound A is preferably greater than the maximum absorption wavelength of photosensitive compound B.

[0402] The maximum absorption wavelength of a photosensitive compound is defined as the wavelength located on the longest wavelength side within the wavelength range of 190–450 nm.

[0403] Photosensitive compound A is a compound that causes a change in the solubility of the photocurable film relative to the developing solution during the first exposure step described above.

[0404] Specifically, the photosensitive compound A is preferably a compound that undergoes a chemical change (generating free radicals, generating acids, generating bases, etc.) during the first exposure step and causes a change in the solubility of the photocurable film relative to the developer along with the aforementioned structural change, and more preferably a compound that generates free radicals during the first exposure step.

[0405] Furthermore, photosensitive compound A is preferably a photopolymerization initiator, a photoacid generator, or a photoalkali generator.

[0406] [Photopolymerization initiator]

[0407] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0408] The photoradical polymerization initiator is a compound that conforms to the above-mentioned compounds that generate free radicals through the first exposure process.

[0409] -Photoradical polymerization initiator-

[0410] The photocurable resin composition of the present invention preferably contains a photoradical polymerization initiator as photosensitive compound A.

[0411] For example, by performing free radical polymerization using a photocurable resin composition containing a photoradical polymerization initiator and at least one of a specific resin containing vinyl unsaturated bonds with free radical polymerization properties and a free radical crosslinking agent described later, the solubility of the exposed portion of the photocurable film relative to the developer decreases, thus enabling the formation of a negative pattern.

[0412] There are no particular limitations on the photoradical polymerization initiator; for example, it can be appropriately selected from known compounds. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can be an active agent that interacts with the photoexcited sensitizer and generates active free radicals.

[0413] The photoradical polymerization initiator preferably contains at least one that has a strength of at least about 50 L / mol for light in the wavelength range of about 300–800 nm (preferably 330–500 nm). -1 / cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) and ethyl acetate solvent at a concentration of 0.01 g / L.

[0414] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0415] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0416] Hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can also be used.

[0417] As hydroxyacetophenone-based initiators, IRGACURE 184 (IRGACURE is a registered trademark), Irgacure 1173, DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF), Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resisns) can be used.

[0418] As an aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resins BV) can be used.

[0419] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, whose maximum absorption wavelength is matched to light sources of wavelengths such as 365 nm or 405 nm, can also be used.

[0420] Examples of acylphosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Furthermore, commercially available products such as IRGACURE-819 or IRGACURE-TPO (trade names: both manufactured by BASF), Omnirad 819 or Omnirad TPO (both manufactured by IGM Resins BV) can be used.

[0421] Examples of metallocene compounds include IRGACURE-784 (manufactured by BASF).

[0422] Oxime compounds are preferred as photoradical polymerization initiators. Using oxime compounds can further and more effectively improve exposure latitude. Oxime compounds have a wide exposure latitude (exposure margin) and also function as photocuring accelerators, making them particularly preferred.

[0423] As specific examples of oxime compounds, compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, and Japanese Patent Application Publication No. 2006-342166 can be used.

[0424] Preferred oxime compounds include, for example, compounds with 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 photocurable resin compositions of the present invention, oxime compounds (oxime-based photoradical polymerization initiators) are particularly preferred as photoradical polymerization initiators. Oxime compounds serving as photoradical polymerization initiators have an intramolecular linker represented by >C=NOC(=O)-.

[0425] [Chemical Formula 11]

[0426]

[0427] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, the photoradical polymerization initiator 2 disclosed in Japanese Patent Application Publication No. 2012-014052) are also preferred. Furthermore, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLSNCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co.,Ltd.) can also be used.

[0428] Oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include the compound described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471.

[0429] Examples of preferred oxime compounds include oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and oxime compounds with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061.

[0430] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0431] More preferably, the photoradical polymerization initiator is a trihalomethane triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, it is a compound selected from at least one of the following: trihalomethane triazine compound, α-amino ketone compound, oxime compound, triarylimidazolium dimer, or benzophenone compound. More preferably, it is a metallocene compound or an oxime compound. More preferably, it is an oxime compound.

[0432] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by fusion of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; and benzyl derivatives such as benzyl dimethyl ketal. Compounds represented by the following formula (I) can also be used.

[0433] [Chemical Formula 12]

[0434]

[0435] In equation (I), R I00 The alkyl group having 1 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, the alkoxy group having 1 to 12 carbon atoms, the phenyl group, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the halogen atom, the cyclopentyl group, the cyclohexyl group, the alkenyl group having 2 to 12 carbon atoms, the alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and the alkyl group having 1 to 4 carbon atoms, are at least one substituted phenyl or biphenyl groups. I01 For the group represented by formula (II), or for the group with R I00 The same group, R I02 ~R I04 Each is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[0436] [Chemical Formula 13]

[0437]

[0438] In the formula, R I05 ~R I07 R in equation (I) above I02 ~RI04 same.

[0439] Furthermore, the photoradical polymerization initiator can also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469.

[0440] When the photocurable resin composition contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator relative to the total solids content of the photocurable resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photoradical polymerization initiator may contain only one type or two or more types. When two or more photoradical polymerization initiators are contained, it is preferable that their total content falls within the above-mentioned range.

[0441] In addition, since photopolymerization initiators sometimes also function as thermal polymerization initiators, crosslinking based on photopolymerization initiators is sometimes carried out by heating in an oven or heating plate.

[0442] [Photo-acid generator]

[0443] The photocurable resin composition of the present invention preferably also contains a photoacid generator as photosensitive compound A.

[0444] By including a photoacid-generating agent, for example, generating acid in the exposed portion of the photocurable film, the solubility of the developer (e.g., an alkaline aqueous solution) in the exposed portion is increased, and a positive relief pattern in which the exposed portion is removed by the developer can be obtained.

[0445] Furthermore, it is also possible to configure the photocurable resin composition to contain a photoacid generator and a crosslinking agent (described later), for example, by using the acid generated in the exposed portion to promote the crosslinking reaction of the crosslinking agent, making the exposed portion less susceptible to removal by the developing solution than the unexposed portion. Based on these methods, negative relief patterns can be obtained.

[0446] As a photoacid generator, there are no particular limitations as long as it produces acid through exposure. Examples include quinone diazide compounds, diazonium salts, phosphonium salts, sulfonium salts, iodine salts and other ononium salt compounds, imide sulfonates, oxime sulfonates, diazonium disulfones, disulfones, o-nitrobenzyl sulfonates and other sulfonate compounds.

[0447] Examples of quinone diazide compounds include compounds in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, compounds in which the sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, and compounds in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy polyamino compound via at least one of an ester bond and a sulfonamide bond. In this invention, for example, it is preferable that at least 50 mol% of the functional groups of these polyhydroxy and polyamino compounds are substituted with quinone diazide.

[0448] In this invention, 5-naphthoquinone diazidesulfonyl and 4-naphthoquinone diazidesulfonyl are both preferably used as quinone diazides. The 4-naphthoquinone diazidesulfonyl ester compound has absorption in the i-ray region of a mercury lamp, and is therefore suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazidesulfonyl ester compound extends to the g-ray region of a mercury lamp, and is therefore suitable for g-ray exposure. In this invention, 4-naphthoquinone diazidesulfonyl ester and 5-naphthoquinone diazidesulfonyl ester compounds are preferably selected according to the wavelength of exposure. Furthermore, a naphthoquinone diazidesulfonyl ester compound may contain both 4-naphthoquinone diazidesulfonyl and 5-naphthoquinone diazidesulfonyl groups in the same molecule, or it may contain both 4-naphthoquinone diazidesulfonyl ester and 5-naphthoquinone diazidesulfonyl ester compounds.

[0449] The aforementioned naphthoquinone diazide compounds can be synthesized via esterification of compounds with phenolic hydroxyl groups and quinone diazidesulfonic acid compounds, and can also be synthesized using known methods. By using these naphthoquinone diazide compounds, resolution, sensitivity, and residual film yield are further improved.

[0450] Examples of onium salt compounds or sulfonate compounds include compounds described in paragraphs 0064 to 0122 of Japanese Patent Application Publication No. 2008-013646.

[0451] In addition, commercially available products can be used as photoacid generators. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (all manufactured by IGMresins BV), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF Corporation).

[0452] When a photoacid-generating agent is included, its content relative to the total solids content of the photocurable resin composition of the present invention 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. The photoacid-generating agent may be only one type or may contain two or more types. When two or more photoacid-generating agents are included, their total content is preferably within the above-mentioned range.

[0453] [Photo-induced alkali production agent]

[0454] The photocurable resin composition of the present invention may contain a photoalkali-generating agent as photosensitive compound A.

[0455] By including a photocurable resin composition containing a photoalkali-generating agent and a crosslinking agent (described later), for example, the exposed areas are less susceptible to removal by the developing solution than the unexposed areas due to the alkali generated in the exposed areas promoting the cyclization of a specific resin and the crosslinking reaction of the crosslinking agent. Based on these methods, negative relief patterns can be obtained.

[0456] As a photoalkali-generating agent, there are no particular limitations as long as alkali is produced through exposure, and known photoalkali-generating agents can be used.

[0457] For example, M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006) describe ionic compounds in which the base component is neutralized by salt formation, such as transition metal compound complexes, compounds with structures such as ammonium salts, and compounds in which the amidine component is potentialized by forming salts with carboxylic acids; and nonionic compounds in which the base component is potentialized by carbamate bonds or oxime bonds, such as carbamate derivatives, oxime derivatives, and acyl compounds.

[0458] In this invention, more preferred examples of photoalkali-generating agents include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives.

[0459] There are no particular limitations on the alkaline substances produced from photoalkali-producing agents. Examples include compounds with amino groups, especially polyamines such as monoamines and diamines, as well as amidines.

[0460] From the viewpoint of imidization rate, the aforementioned basic substance preferably has a larger pKa in DMSO (dimethyl sulfoxide), a conjugate acid. The pKa is preferably 1 or higher, more preferably 3 or higher. There is no particular upper limit to the pKa, but it is preferably 20 or lower.

[0461] Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and can be referenced to the values ​​described in Determining Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these publications, the values ​​calculated from the structural formula using ACD / pKa software (manufactured by ACD / Labs) will be used as the pKa.

[0462] From the viewpoint of the storage stability of the photocurable resin composition, the photoalkali-generating agent is preferably a salt-free agent in its structure, and preferably one in which the nitrogen atom of the alkali moiety produced in the photoalkali-generating agent has no charge. As a photoalkali-generating agent, it is preferable that the produced alkali is latent via covalent bonds, and the alkali generation mechanism is preferably one in which the covalent bonds between the nitrogen atom of the produced alkali moiety and its adjacent atoms are broken. If the photoalkali-generating agent is salt-free in its structure, it can be made neutral, thus resulting in better solvent solubility and an extended shelf life. For these reasons, the amine produced from the photoalkali-generating agent used in this invention is preferably a primary or secondary amine.

[0463] Furthermore, from the viewpoint of the pattern's resistance to chemicals, a photoalkali-generating agent that contains salt in its structure is preferred.

[0464] Furthermore, considering the above reasons, as a photo-alkali-generating agent, it is preferable that the generated alkali is latent using covalent bonds, and more preferably using amide bonds, carbamate bonds, or oxime bonds.

[0465] Examples of photoalkali-generating agents of the present invention include, for example, those with a cinnamamide structure disclosed in Japanese Patent Application Publication No. 2009-080452 and International Patent Application Publication No. 2009 / 123122; those with a carbamate structure disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747; and those with an oxime structure or a carbamoyl oxime structure disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581. However, the invention is not limited to these examples. In addition, known photoalkali-generating agent structures can be used.

[0466] In addition, as photo-alkali-generating agents, examples include compounds described in paragraphs 0185-0188, 0199-0200 and 0202 of Japanese Patent Application Publication No. 2012-093746, compounds described in paragraphs 0022-0069 of Japanese Patent Application Publication No. 2013-194205, compounds described in paragraphs 0026-0074 of Japanese Patent Application Publication No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010 / 064631.

[0467] Alternatively, commercially available products can be used as photo-alkali-generating agents. Examples of commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by FUJIFILM WakoPure Chemical Corporation), A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0468] When a photoalkali-generating agent is included, its content relative to the total solids content of the photocurable resin composition of the present invention 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. The photoalkali-generating agent may be only one type or may contain two or more types. When two or more photoalkali-generating agents are included, their total content is preferably within the above-mentioned range.

[0469] <Photosensitive compound B>

[0470] In the pattern forming method of the present invention, the photocurable resin composition includes a photosensitive compound B, which is sensitive to the exposure wavelength in the second exposure step described above.

[0471] The sensitivity of photosensitive compound B to the exposure wavelength in the second exposure step described above can be determined by the same method as the method for determining whether it has sensitivity described in the description of photosensitive compound A.

[0472] In the first approach, the photosensitive compound B can be the same photopolymerization initiator, photoacid generator, or photoalkali generator as the aforementioned photosensitive compound A.

[0473] The photosensitive compound B can be a compound with the same exposure wavelength as the compound selected as the photosensitive compound A, and preferably a compound with a different exposure wavelength.

[0474] As an example, when a photoradical polymerization initiator with sensitivity around 365 nm is used as photosensitive compound A, a photoalkali-generating agent with sensitivity around 254 nm can be used as photosensitive compound B.

[0475] Furthermore, as another example, when a photoalkali-generating agent with sensitivity around 365 nm is used as photosensitive compound A, it is also possible to use a photoacid-generating agent with sensitivity around 216 nm as photosensitive compound B.

[0476] In a second embodiment of the photocurable resin composition of the present invention, the difference between the maximum absorption wavelength of photosensitive compound A and the maximum absorption wavelength of photosensitive compound B is as described above.

[0477] The maximum absorption wavelength of photosensitive compound B is preferably 190–550 nm, more preferably 200–550 nm, and even more preferably 200–450 nm.

[0478] The maximum absorption wavelength of photosensitive compound B can be determined by the method described above.

[0479] In a second embodiment of the photocurable resin composition, the photosensitive compound B can be a compound that is the same as the photopolymerization initiator, photoacid generator, or photoalkali generator as the photosensitive compound A described above, and whose maximum absorption wavelength is more than 100 nm away from that of the compound selected as photosensitive compound A.

[0480] As an example, when a photoradical polymerization initiator with a maximum absorption wavelength around 365 nm is used as photosensitive compound A, a photoalkali-generating agent with a maximum absorption wavelength around 254 nm can be used as photosensitive compound B.

[0481] Furthermore, as another example, when a photoalkali-generating agent with sensitivity around 365 nm is used as photosensitive compound A, it is also possible to use a photoacid-generating agent with sensitivity around 216 nm as photosensitive compound B.

[0482] When a photopolymerization initiator, photoacid generator, or photoalkali generator is used as photosensitive compound B, the preferred content of these compounds is the same as the preferred content of these compounds when used as photosensitive compound A.

[0483] Furthermore, the preferred combination of photosensitive compound A and photosensitive compound B is as described in methods 1 to 5 above.

[0484] <Solvent>

[0485] The photocurable resin composition of the present invention preferably contains a solvent.

[0486] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

[0487] Furthermore, cyclic hydrocarbons, ureas, alcohols, and other compounds are preferred.

[0488] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid)). Esters, ethyl 3-ethoxypropionate, etc.), 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, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. are suitable esters.

[0489] Examples of suitable ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0490] Examples of suitable ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

[0491] Examples of preferred aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

[0492] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0493] Examples of suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0494] Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone are preferred ureas.

[0495] Examples of 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.

[0496] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0497] In this invention, a solvent preferably selected from 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 mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

[0498] Alternatively, it is particularly preferred to use N-methyl-2-pyrrolidone and ethyl lactate simultaneously.

[0499] From the viewpoint of coatability, the solvent content is preferably set to an amount where the total solids concentration of the photocurable resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass. The solvent content can be adjusted according to the required thickness of the coating and the coating method.

[0500] The solvent may contain only one type or two or more types. When there are two or more solvents, it is preferable that their total number is within the range mentioned above.

[0501] <Cross-linking agent>

[0502] The photocurable resin composition of the present invention preferably contains a crosslinking agent.

[0503] The crosslinking agent is preferably a crosslinking agent having the group that promotes bonding reaction with other groups by photosensitization by the photosensitive compound B in the second exposure step described above, as described in condition 2 above.

[0504] Examples of crosslinking agents include free radical crosslinking agents and other crosslinking agents.

[0505] <Free radical crosslinking agent>

[0506] The photocurable resin composition of the present invention preferably further comprises a free radical crosslinking agent.

[0507] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, these free radical polymerizable groups contain vinyl unsaturated bonds. Examples of groups containing vinyl unsaturated bonds include vinyl, allyl, vinylphenyl, and (meth)acryloyl groups.

[0508] Among these, the group containing the aforementioned vinyl unsaturated bond is preferably (meth)acryloyl, and from the viewpoint of reactivity, (meth)acryloyloxy is more preferably (meth)acryloyloxy.

[0509] The free radical crosslinking agent can be a compound having one or more ethylene unsaturated bonds, and more preferably a compound having two or more bonds.

[0510] The compound having two ethylene unsaturated bonds is preferably a compound having two groups containing the aforementioned ethylene unsaturated bonds.

[0511] Furthermore, from the viewpoint of the film strength of the obtained pattern, the photocurable resin composition of the present invention preferably contains a compound having three or more vinyl unsaturated bonds as a free radical crosslinking agent. As the compound having three or more vinyl unsaturated bonds, it is preferably a compound having 3 to 15 vinyl unsaturated bonds, more preferably a compound having 3 to 10 vinyl unsaturated bonds, and even more preferably a compound having 3 to 6 vinyl unsaturated bonds.

[0512] Furthermore, compounds having three or more of the aforementioned ethylene unsaturated bonds are preferably compounds having three or more groups containing the aforementioned ethylene unsaturated bonds, more preferably compounds having three to 15 groups, even more preferably compounds having three to 10 groups, and particularly preferably compounds having three to six groups.

[0513] Furthermore, from the viewpoint of the film strength of the obtained pattern, the photocurable resin composition of the present invention preferably includes compounds having two vinyl unsaturated bonds and compounds having three or more of the above vinyl unsaturated bonds.

[0514] The molecular weight of the free 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 free radical crosslinking agent is preferably 100 or more.

[0515] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Additionally, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as another example, compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can be used to replace the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0516] Furthermore, the free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples 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, glycerol, or trimethylolethane, which are added to polyfunctional alcohols with ethylene oxide or propylene oxide followed by (meth)acrylate addition. Esterified compounds, (meth)acrylate carbamates disclosed in Japanese Patent Application Publications Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates disclosed in Japanese Patent Application Publications Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth)acrylic acid, and other multifunctional acrylates or methacrylates; and mixtures thereof. Furthermore, compounds disclosed in paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2008-292970 are preferred. Also, examples include multifunctional (meth)acrylates obtained by reacting a multifunctional carboxylic acid with a compound having a cyclic ether group and an vinyl unsaturated bond, such as glycidyl (meth)acrylate.

[0517] Furthermore, as preferred free radical crosslinking agents besides those mentioned above, compounds having a fluorene ring and having two or more groups with ethylene unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resins, can also be used.

[0518] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, as well as vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, can be cited. Compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, compounds described as photocurable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0519] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 may also be used, and these contents are incorporated in this specification.

[0520] Furthermore, the following compound, described in Japanese Patent Application Publication No. 10-062986 as formula (1) and formula (2) along with its specific examples, can also be used as a free radical crosslinking agent. This compound is a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then esterifying it with (meth)acrylate.

[0521] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and this information is incorporated into this specification.

[0522] Preferred free radical crosslinking agents are 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., and 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., and A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues. These oligomer types can also be used.

[0523] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methacrylate with four ethoxy groups, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six pentyli groups, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyryliyl groups, manufactured by Nippon Kayaku Co., Ltd.; 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.). (Manufactured by 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.), BLEMMERPME400 (manufactured by NOF CORPORATION.), etc.

[0524] As a free radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide backbone as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0525] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphate groups. Among the free radical crosslinking agents having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and more preferably, free radical crosslinking agents that react the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with non-aromatic carboxylic anhydrides to give it acid groups are preferred. Particularly preferred are free radical crosslinking agents that react the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with non-aromatic carboxylic anhydrides to give it acid groups, wherein the aliphatic polyhydroxy compound is a pentaerythritol or dipentaerythritol compound. As commercially available products, for example, M-510, M-520, etc., are used by TOAGOSEI CO., Ltd. to manufacture polybasic acid-modified acrylic oligomers.

[0526] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1–40 mg KOH / g, particularly preferably 5–30 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid value was determined according to the description in JIS K 0070:1992.

[0527] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses a difunctional methacrylate or acrylate.

[0528] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dimethacrylate can be used. Acrylic esters, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0529] Additionally, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the molecular weight of the polyethylene glycol chain is around 200.

[0530] From the viewpoint of controlling the elastic modulus of the accompanying pattern and suppressing warpage, a monofunctional free radical crosslinking agent can preferably be used as a free radical crosslinking agent in the photocurable resin composition of the present invention. As a monofunctional free radical crosslinking agent, preferably used are n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, benzyl acrylate, phenoxyethyl acrylate, N-hydroxymethyl methacrylamide, glycidyl acrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and other methacrylic acid derivatives; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; allyl compounds such as allyl glycidyl ether, diallyl phthalate, and trimellitic acid trimellitate. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, it is preferred to be a compound with a boiling point of 100°C or higher under normal pressure.

[0531] When a free radical crosslinking agent is included, its content relative to the total solids content of the photocurable resin composition of the present invention is preferably greater than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0532] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used simultaneously, it is preferable that their combined dosage is within the range mentioned above.

[0533] <Other crosslinking agents>

[0534] The photocurable resin composition of the present invention preferably contains other crosslinking agents different from the free radical crosslinking agents described above.

[0535] In this invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. Preferably, they are compounds having multiple groups within the molecule that promote (the formation of covalent bonds between the crosslinking agent and other compounds in the composition or their reaction products) a reaction facilitated by the photosensitivity of the photosensitive compound A or photosensitive compound B. More preferably, they are compounds having multiple groups within the molecule that promote (the formation of covalent bonds between the crosslinking agent and other compounds in the composition or their reaction products) a reaction facilitated by the action of an acid or base.

[0536] The aforementioned acid or alkali is an acid or alkali produced from photosensitive compound A or photosensitive compound B, i.e., photoacid generator or photoalkali generator, in the first exposure step or the second exposure step.

[0537] As other crosslinking agents, it is preferred to be a compound having at least one group selected from hydroxymethyl and alkoxymethyl, more preferably a compound having a structure in which at least one group selected from hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom.

[0538] Other crosslinking agents include, for example, compounds that react amino-containing compounds such as melamine, glycourea, urea, alkylene urea, and benzoguanidine with formaldehyde, or formaldehyde with an alcohol, and replace the hydrogen atoms of the aforementioned amino groups with hydroxymethyl or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, these compounds can be oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds.

[0539] As for the aforementioned amino-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycourea, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents.

[0540] Among these, the photocurable 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 glycourea-based crosslinking agents and melamine-based crosslinking agents described later.

[0541] As a compound containing at least one of the alkoxymethyl and acylmethyl groups of the present invention, examples of compounds in which the alkoxymethyl or acylmethyl group is directly substituted on the nitrogen atom of an aromatic group or a urea structure described below, or on a triazine, can be cited as structural examples.

[0542] The alkoxymethyl or acylmethyl groups in the above compounds preferably have 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.

[0543] The total number of alkoxymethyl and acylmethyl groups in the above-mentioned compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0544] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0545] [Chemical Formula 14]

[0546]

[0547] R 100 Indicates alkyl or acyl groups.

[0548] R 101 and R 102Organic groups that are monovalent can bond together to form a ring.

[0549] As compounds in which alkoxymethyl or acylmethyl groups are directly substituted for aromatic groups, examples include various compounds of the following general formula.

[0550] [Chemical Formula 15]

[0551]

[0552] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each can be independently represented by an alkyl or acyl group, R 103 Decomposition by the action of hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or acids indicates the formation of a base-soluble group (e.g., a group that is removed by the action of an acid, or a group consisting of -C(R)). 4 )2COOR 5 The group represented (R) 4 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 5 This indicates a group that is released through the action of an acid.

[0553] R 105 Each can be independently represented as an alkyl or alkenyl group, with a, b, and c each being 1 to 3, d being 0 to 4, e being 0 to 3, f being 0 to 3, a+d being 5 or less, b+e being 4 or less, and c+f being 4 or less.

[0554] Regarding groups that decompose under the action of acid and produce alkali-soluble groups, groups that are released under the action of acid, and groups derived from -C(R) 4 )2COOR 5 The R5 in the indicated group, for example, can be -C(R36)(R 37 (R) 38 ), -C(R 36 (R) 37 (OR) 39 ), -C(R 01 (R) 02 (OR) 39 )wait.

[0555] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37 They can bond together to form a ring.

[0556] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0557] The aforementioned alkyl groups can be either straight-chain or branched.

[0558] The cycloalkyl group described above is preferably a cycloalkyl group with 3 to 12 carbon atoms, and more preferably a cycloalkyl group with 3 to 8 carbon atoms.

[0559] The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures such as fused rings.

[0560] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0561] The aralkyl group is preferably an aralkyl group with 7 to 20 carbon atoms, and more preferably an aralkyl group with 7 to 16 carbon atoms.

[0562] The aforementioned aryl group refers to an aryl group substituted with an alkyl group, and the preferred manner of these alkyl and aryl groups is the same as that of the aforementioned alkyl and aryl groups.

[0563] The alkenyl group is preferably an alkenyl group with 3 to 20 carbon atoms, and more preferably an alkenyl group with 3 to 16 carbon atoms.

[0564] Furthermore, these groups may also have known substituents within the scope of achieving the effects of the present invention.

[0565] R 01 and R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

[0566] These groups are preferably tertiary alkyl esters, acetals, cumyl esters, enols, etc. Tertiary alkyl esters and acetals are more preferred.

[0567] As compounds having an alkoxymethyl group, specific examples include the following structures. Compounds having an acylmethyl group include those in which the alkoxymethyl group of the following compounds is replaced with an acylmethyl group. Compounds having an alkoxymethyl group or an acylmethyl group intramolecularly include, but are not limited to, the following compounds.

[0568] [Chemical Formula 16]

[0569]

[0570] [Chemical Formula 17]

[0571]

[0572] Compounds containing at least one of alkoxymethyl and acylmethyl groups can be commercially available compounds or compounds synthesized by known methods.

[0573] From the viewpoint of heat resistance, alkoxymethyl or acylmethyl is preferably a compound that is directly substituted on an aromatic ring or a triazine ring.

[0574] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0575] Specific examples of urea-based crosslinking agents include monohydroxymethylated glycourea, dihydroxymethylated glycourea, trihydroxymethylated glycourea, tetrahydroxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetramethoxymethylated glycourea, monomethoxymethylated glycourea, dimethoxymethylated glycourea, trimethoxymethylated glycourea, tetraethoxymethylated glycourea, monopropoxymethylated glycourea, dipropoxymethylated glycourea, tripropoxymethylated glycourea, tetrapropoxymethylated glycourea, monobutoxymethylated glycourea, dibutoxymethylated glycourea, tributoxymethylated glycourea, or tetrabutoxymethylated glycourea, etc.

[0576] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0577] Monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc., are vinylurea-based crosslinking agents.

[0578] Acrylurea crosslinking agents such as monohydroxymethylated acrylate, dihydroxymethylated acrylate, monomethoxymethylated acrylate, dimethoxymethylated acrylate, monoethoxymethylated acrylate, diethoxymethylated acrylate, monopropoxymethylated acrylate, dipropoxymethylated acrylate, monobutoxymethylated acrylate, or dibutoxymethylated acrylate.

[0579] 1,3-Di(methoxymethyl)4,5-dihydroxy-2-imidazolinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc.

[0580] Specific examples of benzoguanidine-based crosslinking agents include, for instance, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0581] In addition, as a compound having at least one group selected from hydroxymethyl and alkoxymethyl, a compound in which at least one group selected from hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can also be used.

[0582] Specific examples of these compounds include terephthalic acid, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4”-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-terephthalic acid], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0583] Other crosslinking agents can be commercially available products. Preferred commercially available products include 46DMOC, 46DMOEP (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, same below) 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.

[0584] Furthermore, the photocurable resin composition of the present invention preferably includes at least one compound selected from epoxy compounds, oxetane compounds and benzoxazine compounds as other crosslinking agents.

[0585] [Epoxy compounds (compounds containing epoxy groups)]

[0586] As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C, and because no dehydration reaction originating from cross-linking occurs, film shrinkage is less likely to occur. Therefore, the presence of an epoxy compound can effectively suppress low-temperature curing and warping of the photocurable resin composition.

[0587] The epoxy compound preferably contains a poly(ethylene oxide) group. This further reduces the elastic modulus and suppresses warping. The poly(ethylene oxide) group refers to a group in which ethylene oxide has two or more repeating units, preferably 2 to 15 repeating units.

[0588] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type 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, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy-containing silicones such as polymethyl (epoxypropoxypropyl)siloxane, but are not limited to these. Specifically, 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 (registered trademark) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, and EPICLON (registered trademark) EXA-4822 (these are product names, DIC). (manufactured by CORPORATION), RIKARESIN (registered trademark) BEO-60E (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are product names, manufactured by ADEKA Corporation), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, CELVENUS B0134, B0177 (the above are product names, manufactured by Daicel) (Manufactured by Nippon Kayaku Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[0589] Furthermore, the following compounds are also preferably used.

[0590] [Chemical Formula 18]

[0591]

[0592] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0593] Among the above structures, considering both heat resistance and improved ductility, n is preferably 1 to 2 and m is preferably 3 to 7.

[0594] [Oxycyclic butane compounds (compounds containing an oxycyclic butyl group)]

[0595] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetane-butyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetane-butyl)methyl] ester. Specifically, the ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be preferably manufactured using TOAGOSEI CO.,LTD., and these can be used alone or in mixtures of two or more.

[0596] [Benzoxazine compounds (compounds containing a benzoxazole group)]

[0597] Benzooxazine compounds are preferred because their crosslinking reaction, which originates from ring-opening addition, does not produce degassing during curing, thereby reducing thermal shrinkage and inhibiting warping.

[0598] Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resin, and phenolic varnish-type dihydrobenzoxazine compounds. These can be used alone or in combination of two or more.

[0599] The content of other thermal crosslinking agents relative to the total solids content of the photocurable resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may be two or more types. When two or more other thermal crosslinking agents are contained, it is preferable that their total content falls within the above-mentioned range.

[0600] <Thermal polymerization initiator>

[0601] The photocurable resin 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 through thermal energy, initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, for example, in cases where the patterning method of the present invention includes a heating step, the polymerization reaction of the resin and the polymerizable compound can be carried out, thereby further improving chemical resistance.

[0602] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as initiators of thermal free radical polymerization.

[0603] When a thermal polymerization initiator is included, its content relative to the total solids content of the composition of the present invention 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. The thermal polymerization initiator may be only one type or may contain two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0604] <Heat-generating acid agents>

[0605] The photocurable resin composition of the present invention may also contain a heat-generating acid agent.

[0606] For example, when the pattern forming method of the present invention includes a heating step, the thermally generated acid agent has the effect of generating acid by heating and promoting the crosslinking reaction of at least one compound selected from compounds having hydroxymethyl, alkoxymethyl or acylmethyl, epoxy compounds, cyclobutane compounds and benzoxazine compounds.

[0607] The thermal decomposition start temperature of the thermal acid-generating agent is preferably 50°C to 270°C, more preferably 50°C to 250°C. Furthermore, if a substance that does not generate acid during drying (pre-baking: approximately 70°C to 140°C) after the composition is coated onto the substrate but generates acid during the final heating (curing: approximately 100°C to 400°C) after pattern formation during subsequent exposure and development is selected as the thermal acid-generating agent, the decrease in sensitivity during development can be suppressed, and therefore this is preferred.

[0608] When the heat-generating acid agent is placed in a pressure-resistant capsule and heated to 500°C at a rate of 5°C / minute, the peak temperature of the lowest pyrolysis peak is determined as the thermal decomposition initiation temperature.

[0609] Examples of equipment used for determining the onset temperature of thermal decomposition include the Q2000 (manufactured by TA Instruments).

[0610] The acid produced from the thermally generated acid is preferably a strong acid, such as aryl sulfonic acids like p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids like methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or haloalkyl sulfonic acids like trifluoromethanesulfonic acid. Examples of such thermally generated acid agents include the substance described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

[0611] From the viewpoint of minimizing residue in organic membranes and minimizing degradation of membrane properties, the preferred thermal acid-generating agent is a substance that produces alkyl sulfonic acids or haloalkyl sulfonic acids with 1 to 4 carbon atoms. Preferred examples include methanesulfonic acid (4-hydroxyphenyl)dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium, methanesulfonic acid benzyl(4-hydroxyphenyl)methylsulfonium, methanesulfonic acid benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium, and trifluoromethane. Sulfonic acid (4-hydroxyphenyl)dimethylsulfonium, trifluoromethanesulfonate (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, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0612] Furthermore, the compound described in Japanese Patent Application Publication No. 2013-167742, No. 0059, is preferred as a thermal acid-producing agent.

[0613] The content of the heat-generating acid agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the resin. By containing 0.01 parts by mass or more, the cross-linking reaction is promoted, thereby further improving the mechanical properties and chemical resistance of the organic film. Furthermore, from the viewpoint of the electrical insulation of the organic film, it 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.

[0614] <Onion salt>

[0615] The compositions of the present invention preferably contain onium salts.

[0616] In particular, when other resins contain polyimide precursors, the composition preferably contains onium salts.

[0617] There are no particular limitations on the types of onium salts, but ammonium salts, imine salts, sulfonium salts, iodine salts, or phosphonium salts are preferred examples.

[0618] Among these, from the viewpoint of high thermal stability, ammonium salts or imine salts are preferred, and from the viewpoint of compatibility with polymers, sulfonium salts, iodine salts, or phosphonium salts are preferred.

[0619] Furthermore, onium salts are salts of cations and anions with onium structures, and these cations and anions may or may not be bonded by covalent bonds.

[0620] That is, the onium salt can be an intramolecular salt having a cation and anion portion within the same molecular structure, or it can be an intermolecular salt in which cation molecules and anion molecules of different molecular weights are ionicly bonded, preferably an intermolecular salt. Furthermore, in the composition of the present invention, the aforementioned cation portion or cation molecule and the aforementioned anion portion or anion molecule can be bonded by ionic bonds or can be dissociated.

[0621] The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodocation, or a phosphonium cation, and more preferably at least one cation selected from tetraalkylammonium cation, sulfonium cation, and iodocation.

[0622] The onium salt used in this invention can also be a thermal alkali-generating agent.

[0623] Thermal alkali-producing agents refer to compounds that produce alkali by heating. For example, acidic compounds that produce alkali when heated to above 40°C can be cited.

[0624] Examples of onnnage salts include those described in paragraphs 0122 to 0138 of International Publication No. 2018 / 043262. Furthermore, onnnage salts used in the field of polyimide precursors can also be used without particular limitation.

[0625] When the composition of the present invention contains an onium salt, the content of the onium salt relative to the total solid content of the composition of the present invention is preferably 0.1 to 50% by mass. 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 can be 5% by mass or less, or 4% by mass or less.

[0626] One or more onion salts can be used. When using two or more, it is preferable that the total amount is within the range mentioned above.

[0627] <Heat-generating alkali agent>

[0628] The compositions of the present invention may contain a thermally generated alkali agent.

[0629] In particular, when the composition contains a polyimide precursor as another resin, the composition preferably contains a thermal alkali-generating agent.

[0630] The thermal alkali-generating agent can be a compound that conforms to the above-mentioned onium salt, or it can be another thermal alkali-generating agent other than the above-mentioned onium salt.

[0631] Examples of bases produced by alkali-producing agents include secondary amines and tertiary amines.

[0632] There are no particular limitations on the alkali-generating agent of the present invention, and known alkali-generating agents can be used. Examples of known alkali-generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0633] Other examples of thermal alkali-generating agents include nonionic thermal alkali-generating agents.

[0634] Compounds represented by formula (B1) or formula (B2) can be cited as nonionic thermal alkali-producing agents.

[0635] [Chemical Formula 19]

[0636]

[0637] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be independently an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Specifically, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb 3 None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to carbon atoms in a hydrocarbon system. Therefore, it is not limited to this definition when the bonded carbon atoms are carbon atoms that form a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0638] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3Preferably, at least one of these contains a cyclic structure, more preferably at least two contain a cyclic structure. The cyclic structure can be any of a monocyclic or fused ring, preferably a monocyclic or a fused ring of two monocyclic rings. The monocyclic ring is preferably a 5-membered or 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.

[0639] More specifically, Rb 1 and Rb 2 Preferably, the substituents are hydrogen atoms, alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), or aralkyl groups (preferably with 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). These groups may have substituents within the range that enables the effects of the present invention. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are 4- to 7-membered nitrogen-containing heterocycles. In particular, Rb 1 and Rb 2 Preferably, it is a straight-chain, branched, or cyclic alkyl group that may have substituents (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), more preferably a cycloalkyl group that may have substituents (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), and even more preferably a cyclohexyl group that may have substituents.

[0640] As Rb 3 Examples of such compounds include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), aralkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), aryl-alkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkoxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Preferably, the compounds are cycloalkyl (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12), aryl, or arylalkoxy. Rb 3 The invention may further contain substituents within the scope of achieving the effects of the invention.

[0641] The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

[0642] [Chemical Formula 20]

[0643]

[0644] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 The meanings are respectively related to Rb in equation (B1). 1 and Rb 2 same.

[0645] Rb 13 The substituents are alkyl (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), and may have substituents within the range that allows the effects of the present invention to be achieved. Rb 13 Preferably, it is an aryl alkyl group.

[0646] Rb 33 and Rb 34 Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0647] Rb 35 The carbon atoms are alkyl (preferably 1 to 24, more preferably 1 to 12, and even more preferably 3 to 8), alkenyl (preferably 2 to 12, more preferably 2 to 10, and even more preferably 3 to 8), aryl (preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 12), aralkyl (preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 12), and preferably aryl.

[0648] The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).

[0649] [Chemical Formula 21]

[0650]

[0651] Rb 11 and Rb 12 The meaning of Rb in equation (B1-1) 11 and Rb 12 same.

[0652] Rb 15 and Rb 16 The atom is hydrogen, alkyl (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), aryl (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen or methyl.

[0653] Rb 17 The carbon atoms are alkyl (preferably 1 to 24, more preferably 1 to 12, and even more preferably 3 to 8), alkenyl (preferably 2 to 12, more preferably 2 to 10, and even more preferably 3 to 8), aryl (preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 12), or aralkyl (preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 12), wherein aryl is preferred.

[0654] The molecular weight of the nonionic thermal alkali-generating agent is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0655] Among the above-mentioned onium salts, the following compounds can be cited as specific examples of compounds that are thermal alkali-generating agents or other specific examples of thermal alkali-generating agents.

[0656] [Chemical Formula 22]

[0657]

[0658] [Chemical Formula 23]

[0659]

[0660] [Chemical Formula 24]

[0661]

[0662] The content of the thermal alkali-generating agent 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 more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or more thermal alkali-generating agents can be used. When two or more are used, the total amount is preferably within the above-mentioned range.

[0663] <Migration Inhibitor>

[0664] The photocurable resin composition of the present invention preferably further comprises a migration inhibitor. By including a migration inhibitor, the migration of metal ions from the metal layer (metal wiring) into the photocurable film can be effectively suppressed.

[0665] There are no particular limitations on the migration inhibitors, and examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds with hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetraazole compounds such as 1H-tetrazole and 5-phenyltetrazole are preferred.

[0666] Alternatively, compounds such as 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and 5-amino-1H-tetrazole can also be used.

[0667] Alternatively, ion trapping agents that capture anions such as halide ions can also be used.

[0668] Other migration inhibitors include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219.

[0669] The following compounds can be cited as specific examples of migration inhibitors.

[0670] [Chemical Formula 25]

[0671]

[0672] When the photocurable resin composition contains a migration inhibitor, the content of the migration inhibitor relative to the total solids content of the photocurable resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0673] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the above range.

[0674] <Polymerization Inhibitor>

[0675] The photocurable resin composition of the present invention preferably contains a polymerization inhibitor.

[0676] Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0677] As polymerization inhibitors, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallnut phenol, 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, etc., may be preferably used. Ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediaminetetraacetic acid (CTA), glycol ether diaminetetraacetic acid (DETA), 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Patent Publication No. 2015 / 125469 can also be used.

[0678] Furthermore, the following compounds (Me is methyl) can be used.

[0679] [Chemical Formula 26]

[0680]

[0681] When the photocurable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the photocurable resin composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass.

[0682] There may be only one type of polymerization inhibitor or two or more types. When there are two or more polymerization inhibitors, it is preferable that their total number is within the above-mentioned range.

[0683] <Metal Adhesion Modifier>

[0684] The photocurable resin composition of the present invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents.

[0685] More specifically, examples include silane coupling agents with alkoxysilyl groups, aluminum-based adhesives, titanium-based adhesives, compounds with sulfonamide structures and compounds with thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, amino compounds, and so on.

[0686] Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014 / 097594. Furthermore, it is preferable to use two or more different silane coupling agents, as described in paragraphs 0050-0058 of Japanese Patent Application Publication No. 2011-128358. Furthermore, the following compounds are preferred as silane coupling agents. In the following formula, Et represents ethyl.

[0687] [Chemical Formula 27]

[0688]

[0689] [Aluminum-based adhesive additives]

[0690] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropylaluminum ethyl acetoacetate.

[0691] Furthermore, as a metal adhesion modifier, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used.

[0692] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting the content above the lower limit, the adhesion between the pattern and the metal layer becomes better; by setting the content below the upper limit, the heat resistance and mechanical properties of the pattern become better. The metal adhesion modifier can be only one type or two or more types. When using two or more types, it is preferable that their total content is within the above range.

[0693] <Other Additives>

[0694] The photocurable resin composition of the present invention can be formulated with various additives as needed, within the range that achieves the effects of the present invention, such as thermally generated acid agents, sensitizers such as N-phenyldiethanolamine, surfactants, chain transfer agents, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-coagulation agents, etc. When incorporating these additives, it is preferable that their total amount is set to 3% by mass or less of the solid content of the photocurable resin composition.

[0695] By appropriately including these components, membrane properties and other characteristics can be adjusted. These components can be found, for example, in Japanese Patent Application Publication No. 2012-003225, paragraph 0183 onwards (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and in Japanese Patent Application Publication No. 2008-250074, paragraphs 0101-0104 and 0107-0109, and these contents are incorporated into this specification.

[0696] [surfactants]

[0697] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0698] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially flowability) during preparation as a coating liquid can be further improved, thereby further improving the uniformity of the coating thickness or the liquid-saving properties. That is, when a film is formed using a composition containing a surfactant, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and enhancing the coatability of the coated surface. Therefore, it is even more preferable to form a film with less thickness variation and uniform thickness.

[0699] Examples of fluorinated surfactants include, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, 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. Fluorinated surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, which are included in this specification. Block polymers can also be used as fluorinated surfactants. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 are included in this specification.

[0700] Fluorinated surfactants can also preferably use fluorinated polymers (comprising repeating units from (meth)acrylate compounds having fluorine atoms and repeating units from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxide or propoxide groups), and the following compounds can also be exemplified as fluorinated surfactants used in this invention.

[0701] [Chemical Formula 28]

[0702]

[0703] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0704] Regarding fluorinated surfactants, fluoropolymers with vinyl unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DICCORPORATION.

[0705] The fluorine content in the fluorinated surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniformity of coating film thickness and liquid-saving properties, and also have good solubility in the composition.

[0706] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-EtsuSilicone Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0707] Examples of hydrocarbon-based surfactants include Pionin A-76, Newkalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, and Pionin P-4050-T (all manufactured by TAKEMOTO OIL & FATCO., LTD).

[0708] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFINE E1010, SURFYNOL 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

[0709] As cationic surfactants, examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0710] As anionic surfactants, examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0711] Surfactants can be used in single-agent or in combination of two or more.

[0712] The surfactant content relative to the total solids content of the composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass.

[0713] [Higher fatty acid derivatives]

[0714] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the resin composition of the present invention to make it biased on the surface of the resin composition of the present invention during the drying process after coating.

[0715] Furthermore, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0716] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above-mentioned range.

[0717] [Thermal polymerization initiator]

[0718] The resin 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 through thermal energy, initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the resin and polymerizable compound can also undergo polymerization, thus further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiator also has the function of initiating polymerization through heat and can be added as a polymerization initiator.

[0719] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be cited as thermal free radical polymerization initiators.

[0720] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may be only one type or may contain two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0721] [Inorganic particles]

[0722] The resin composition of the present invention may contain inorganic microparticles. 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, etc.

[0723] The average particle size of the aforementioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and especially preferably 0.04 to 0.5 μm.

[0724] The average particle size mentioned above is the primary particle size and the volume average particle size. The volume average particle size can be determined by known measurement methods. Specifically, it can be determined by centrifugal sedimentation light transmission, X-ray transmission, laser diffraction and scattering, and dynamic light scattering. The average particle size represents the average value of the particle size distribution and can be measured, for example, by using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

[0725] [Ultraviolet absorber]

[0726] The compositions of the present invention may contain ultraviolet absorbers. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

[0727] 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. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-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.

[0728] Examples of acrylonitrile-based ultraviolet absorbers that can be replaced 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-tetrazoloxypropyl)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; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-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-octoxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0729] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more.

[0730] The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present invention is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less.

[0731] [Organotitanium compounds]

[0732] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0733] Examples of usable organotitanium compounds include those in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0734] Specific examples of organotitanium compounds are shown in I) to VII) below:

[0735] I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred, considering the excellent storage stability of the resin composition and the ability to obtain a good cured pattern. Specific examples include titanium bis(triethanolamine) diisopropoxy titanium, bis(n-butoxy) bis(2,4-glutarate) titanium, diisopropoxy bis(2,4-glutarate) titanium, diisopropoxy bis(tetramethylheptanediol) titanium, and diisopropoxy bis(ethyl acetoacetate) titanium.

[0736] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0737] III) Dioctenoid compounds: such as pentamethylcyclopentadienetrimethoxytitanium, 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-pyrrole-1-yl)phenyl)titanium, etc.

[0738] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzenesulfonate) isopropoxy titanium, etc.

[0739] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0740] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0741] VII) Titanate coupling agents: such as isopropyltridodecylbenzenesulfonyl titanate, etc.

[0742] Among these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) dicarboxylated titanium compound is preferred as the organotitanium compound. In particular, diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

[0743] When an organotitanium compound is incorporated, the amount incorporated relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight. When the amount incorporated is 0.05 parts by weight or more, the cured pattern obtained more effectively exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0744] [Antioxidants]

[0745] The compositions of the present invention may contain antioxidants. The presence of antioxidants as additives improves the stretchability and adhesion to metal materials of the cured film. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Hindered phenolic compounds are preferred. Compounds having substituents at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenolic group and a phosphite group within the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants are also preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKACORPORATION). Furthermore, the antioxidants can also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Moreover, the compositions of the present invention may contain potential antioxidants as needed. As potential antioxidants, examples include compounds in which the site where the antioxidant functions is protected by a protecting group, wherein the protecting group is removed by heating at 100–250 °C or heating at 80–200 °C in the presence of an acid / base catalyst, thereby functioning as an antioxidant. Examples of potential antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219, the contents of which are incorporated herein by reference. Commercially available examples of potential 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 formula (3).

[0746] [Chemical Formula 29]

[0747]

[0748] In general formula (3), R5 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R7 represents an organic group having a 1 to 4 valence, comprising at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0749] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic or phenolic hydroxyl groups present in the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metallic materials.

[0750] To enable simultaneous action on both resin and metal materials, k is more preferably an integer from 2 to 4. Examples of R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may further have substituents. From the viewpoint of solubility in the developer and metal adhesion, alkyl ether or -NH- is preferred, and from the viewpoint of interaction with the resin and metal adhesion based on metal complexation, -NH- is more preferred.

[0751] The following compounds are examples of compounds represented by the general formula (3), but are not limited to the following structures.

[0752] [Chemical Formula 30]

[0753]

[0754] [Chemical Formula 31]

[0755]

[0756] [Chemical Formula 32]

[0757]

[0758] [Chemical Formula 33]

[0759]

[0760] The amount of antioxidant added relative to the resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain effects that improve ductility or adhesion to metal materials even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above-mentioned range.

[0761] [Sensitizer]

[0762] The photocurable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal free radical polymerization initiator, a photofree radical polymerization initiator, etc., thereby generating electron transfer, energy transfer, and heat generation. Consequently, the thermal free radical polymerization initiator or the photofree radical polymerization initiator undergoes a chemical change and decomposes, generating free radicals, acids, or bases.

[0763] Examples of sensitizers include milchnerone, 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, and p-dimethylaminophenylenepropyl dihydrogen ketone. Indanone, p-dimethylaminobenzyl dihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7- Dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamino... Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthyl(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0764] Furthermore, sensitizing pigments can also be used as sensitizers.

[0765] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0766] When the photocurable resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solids content of the photocurable resin composition of the present invention 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. A single sensitizer may be used alone, or two or more may be used simultaneously.

[0767] [Chain transfer agent]

[0768] The photocurable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. As chain transfer agents, for example, compounds having SH, PH, SiH, and GeH in their molecules are used. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferably used.

[0769] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219.

[0770] When the photocurable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the photocurable resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total amount is within the above-mentioned range.

[0771] [Higher fatty acid derivatives]

[0772] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the photocurable resin composition of the present invention to make them biased on the surface of the photocurable resin composition during the drying process after coating.

[0773] Furthermore, the compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used as higher fatty acid derivatives.

[0774] When the photocurable resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives relative to the total solids content of the photocurable resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above range.

[0775] <Regarding restrictions on other substances>

[0776] From the viewpoint of coating surface properties, the moisture content of the photocurable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass.

[0777] From the viewpoint of insulation, the metal content of the photocurable 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 metals include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are included, it is preferable that the total amount of these metals is within the above-mentioned range.

[0778] Furthermore, as a method to reduce unintentionally contained metallic impurities in the photocurable resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the photocurable resin composition of the present invention, filtering the raw materials constituting the photocurable resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0779] Considering its use as a semiconductor material and from the viewpoint of wiring corrosion, the halogen atom content in the photocurable resin composition of the present invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The content of halogen atoms existing in the form of halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. Preferably, the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromide ions, is within the above-mentioned ranges.

[0780] As a container for the photocurable resin composition of the present invention, conventionally known containers can be used. Furthermore, as a container, to prevent impurities from contaminating the raw materials or the photocurable resin composition, multi-layer bottles with an inner wall composed of six layers of six different resins, or bottles with a seven-layer structure formed from the six resins, are preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0781] <Uses of UV-curable resin compositions>

[0782] The photocurable resin composition of the present invention is preferably used to form an interlayer insulating film for a rewiring layer.

[0783] Furthermore, it can also be used for the formation of insulating films or stress-buffered films in electronic devices.

[0784] <Preparation of Photocurable Resin Compositions>

[0785] The photocurable 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 carried out using conventionally known methods.

[0786] Furthermore, filtration using a filter is preferred for removing foreign matter such as dust or particles from the photocurable resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. A filter pre-cleaned with an organic solvent can be used. Multiple filters can be used in parallel or in series during the filtration process. When using multiple filters, filters with different pore sizes or materials can be combined. Various materials can be filtered multiple times. Multiple filtrations can be performed as circulating filtration. Filtration can be performed after pressurization. When filtration is performed after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less.

[0787] In addition to filtration using filters, impurity removal can also be performed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0788] Example

[0789] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0790] <Synthetic Example 1: Synthesis of Polymer E>

[0791] 0.600 g (3.00 mmol) of diphenylamine (hereinafter referred to as "ODA") and 0.883 g (3.00 mmol) of 4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter referred to as "BPDA") were added in a single batch to 8.50 mL of N,N-dimethylacetamide (DMAc). The mixture was stirred at room temperature for 12 hours to obtain a solution of polymer E with high viscosity and transparency. The intrinsic viscosity of the polymer in DMAc was 0.73 dL / g at 30 °C and a concentration of 0.5 g / dL. Furthermore, DMAc was a purified substance obtained by vacuum distillation, while ODA and BPDA were obtained by recrystallization from tetrahydrofuran (THF) and acetic anhydride, respectively.

[0792] <Synthetic Example 2: Synthesis of Polymer A-1>

[0793] 155.1 g of 4,4'-oxyphthalic dianhydride (ODPA) was added to a 2-liter separable flask, along with 131.2 g of ethyl 2-hydroxyethyl acrylate (HEMA) and 400 ml of γ-butyrolactone. The mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was allowed to cool naturally to room temperature and left to stand for 16 hours.

[0794] Next, while stirring for 40 minutes, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture under ice-cold conditions. Then, 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone suspension was added over 60 minutes. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and the mixture was stirred for 1 hour, followed by the addition of 400 ml of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution.

[0795] The obtained reaction solution was added to 3 liters of ethanol to produce a precipitate composed of crude polymer. The crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. This crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The precipitate was filtered and then vacuum dried to obtain powdered polymer A-1. The molecular weight of polymer A-1 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 20,000.

[0796] <Synthetic Example 3: Synthesis of Polymer B-1>

[0797] Instead of 155.1 g of 4,4'-oxyphthalic dianhydride in Synthesis Example 2, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride was used, and the reaction was carried out in the same manner as described in Synthesis Example 2 to obtain polymer B-1. The molecular weight of polymer B-1 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 22,000.

[0798] <Synthetic Example 4: Synthesis of Polymer A-2>

[0799] 20.0 g (64.5 mmol) of 4,4'-oxyphthalic dianhydride (dried at 140 °C for 12 h) and 17.12 g (131.58 mmol) of ethyl 2-hydroxyethyl acrylate (HEMA) were suspended in 50 mL of N-methylpyrrolidone and dried through a molecular sieve. The suspension was heated at 100 °C for 3 h. A clear solution was obtained a few minutes after the start of heating. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Then, the reaction mixture was 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. The viscosity increased during the addition of SOCl2. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 h. Next, a solution of 11.75 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at 20–23 °C. The reaction mixture was then stirred overnight at room temperature. Next, the polyimide precursor was precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, added again to 4 L of water, stirred for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 °C for 3 days to obtain polymer A-2.

[0800] <Synthetic Example 5: Synthesis of Polymer B-2>

[0801] Instead of 20.0 g (64.5 mmol) of 4,4'-oxyphthalic anhydride in Synthesis Example 4, 19.0 g (64.5 mmol) of 3,3'4,4'-biphenyltetracarboxylic acid dianhydride was used, and the reaction was carried out in the same manner as described in Synthesis Example 4 to obtain polymer B-2.

[0802] <Synthetic Example 6: Synthesis of Polymer C>

[0803] In a separable flask, 183.1 g (0.5 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g (0.8 mol) of pyridine were mixed and stirred at room temperature (25 °C) to obtain a homogeneous solution. A solution of 118.0 g (0.4 mol) of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise through a dropping funnel. The separable flask was then cooled in a water bath at 15–20 °C. The addition took 40 minutes, and the maximum temperature of the reaction solution was 30 °C.

[0804] Three hours after the addition was completed, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution. The mixture was stirred and allowed to stand at room temperature for 15 hours, at which point 99% of the total amine terminal groups of the polymer chains were sealed by carboxylcyclohexylamide groups. The reaction rate at this point could be easily calculated by tracking the residual amount of 1,2-cyclohexyldicarboxylic anhydride added using high-performance liquid chromatography (HPLC). Subsequently, the reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer. This polymer was recovered, appropriately washed with water, dehydrated, and then vacuum dried to obtain a crude polybenzoxazole precursor with a weight-average molecular weight of 9,000 (converted from polystyrene) determined by gel permeation chromatography (GPC).

[0805] The crude polybenzoxazole precursor obtained above was redissolved in γ-butyrolactone (GBL), and then treated with cation exchange resin and anion exchange resin. The resulting solution was then added to ion-exchanged water, and the precipitated polymer was filtered, washed with water, and vacuum dried to obtain the purified polybenzoxazole precursor (polymer C).

[0806] <Synthetic Example 7: Synthesis of Polymer D>

[0807] Polymer D was synthesized from pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and 2,2'-bis(trifluoromethyl)benzidine using the same method as that used in the synthesis of PFAA by H Seino et al., J. Polym. Sci., Part A: Polym. Chem., 36, 2261 (1998).

[0808] <Examples and Comparative Examples>

[0809] In each embodiment, the components described in Tables 1 to 4 below were mixed to obtain each photocurable resin composition. Furthermore, in each comparative example, the components described in Table 4 below were mixed to obtain each comparative composition.

[0810] Specifically, the content of the components recorded in Tables 1 to 4 is set as the mass parts recorded in Tables 1 to 4.

[0811] The obtained photocurable resin composition and the comparative composition were subjected to pressure filtration through a polytetrafluoroethylene filter with a filter pore size of 0.8 μm.

[0812] Furthermore, in Tables 1 to 4, a "-" indicates that the composition does not contain that ingredient.

[0813] [Table 1]

[0814]

[0815] [Table 2]

[0816]

[0817] [Table 3]

[0818]

[0819] [Table 4]

[0820]

[0821] The detailed information of each component recorded in Tables 1 to 4 is as follows.

[0822] [Resin]

[0823] • A-1, B-1, A-2, B-2, C~E: Polymers A-1, B-1, A-2, B-2, and C~E synthesized in the above synthesis examples

[0824] [Cross-linking agent]

[0825] F-1: Tetraethylene glycol dimethacrylate

[0826] F-2: Light Ester BP-6EM (manufactured by KyoEisha Chemical Co., Ltd.)

[0827] F-3: Light Ester NP (manufactured by KyoEisha Chemical Co., Ltd.)

[0828] • F-4: Light Ester 1.6HX (manufactured by KYOEISHA CHEMICAL CO.,LTD.)

[0829] • F-5: DAICEL CELLOXIDE CEL2081 (manufactured by DAICEL CORPORATION)

[0830] F-6: Hexamethoxymethylmelamine

[0831] [Sealing agent (silane coupling agent)]

[0832] G-1: N-[3-(triethoxysilyl)propyl]phthalic acid

[0833] G-2: N-[3-(triethoxysilyl)propyl]maleic acid

[0834] G-3: 3-Methacryloxypropyltrimethoxysilane

[0835] G-4: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

[0836] • G-5: A compound represented by the following formula (G-5). In formula (G-5), R represents an ethyl group.

[0837] [Chemical Formula 34]

[0838]

[0839] [Polymerization inhibitor]

[0840] H-1: p-Benzoquinone

[0841] H-2: 4-Methoxyphenol

[0842] H-3: 2-Nitro-1-Naphthol

[0843] [Photopolymerization initiator (photosensitive compound)]

[0844] ·I-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (maximum absorption wavelength: 365nm)

[0845] • I-2: NCI 831 (Maximum Absorption Wavelength: 365nm) (Manufactured by ADEKA Corporation)

[0846] • I-3: Irgacure OXE01 (maximum absorption wavelength: 365nm) (manufactured by BASF)

[0847] • I-4: Irgacure OXE02 (maximum absorption wavelength: 365nm) (manufactured by BASF)

[0848] • I-5: Irgacure 784 (maximum absorption wavelength: 405nm) (manufactured by BASF)

[0849] • I-6: Omnirad 2959 (maximum absorption wavelength: 254nm) (manufactured by BASF)

[0850] • I-7: Omnirad 1173 (maximum absorption wavelength: 254nm) (manufactured by BASF)

[0851] [Photoacid generator (photosensitive compound)]

[0852] • J-1: WPAG-145 (maximum absorption wavelength: 216nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0853] J-2: WPAG-170 (maximum absorption wavelength: 214nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0854] [Photoalkali-producing agents (photosensitive compounds)]

[0855] K-1: {[(4,5-dimethoxy-2-nitrobenzyl)oxy]carbonyl}-2,6-dimethylpiperidine (maximum absorption wavelength: 365nm)

[0856] • K-2: WPBG-018 (maximum absorption wavelength: 365nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0857] • K-3: WPBG-140 (maximum absorption wavelength: 365nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0858] K-4: WPBG-027 (maximum absorption wavelength: ~254nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0859] • K-5: WPBG-165 (maximum absorption wavelength: ~254nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0860] • K-6: WPBG-266 (maximum absorption wavelength: ~254nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0861] • K-7: WPBG-300 (maximum absorption wavelength: ~254nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0862] K-8: WPBG-345 (maximum absorption wavelength: ~254nm) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0863] K-9: O0396 (Maximum Absorption Wavelength: 365nm) (Manufactured by Tokyo Chemical Industry Co., Ltd.)

[0864] [Heat-generated alkali agent]

[0865] L-1: N-cyclohexyl-N,N-dimethyl-N-phenacylammonium Maleate

[0866] [Other additives]

[0867] M-1: 7-Diethylamino-3-ethoxycarbonylcoumarin

[0868] M-2: N-Phenylonamine

[0869] M-3: 2,3,4-Tris(1-oxo-2-diazonaphthoquinon-4-ylsulfonyloxy)benzophenone (2,3,4-tris(1-oxo-2-diazonaphthoquinon-4-ylsulfonyloxy)benzophenone)

[0870] M-4: 1H-tetrazole

[0871] • M-5: A compound represented by the following formula (M-5)

[0872] M-6: 5-Amino-1H-tetrazole

[0873] [Chemical Formula 35]

[0874]

[0875] [Solvent]

[0876] S-1: N-methylpyrrolidone

[0877] S-2: Ethyl lactate

[0878] S-3: γ-Butyrolactone

[0879] S-4: Dimethyl sulfoxide

[0880] S-5: N,N-Dimethylacetamide

[0881] <Evaluation>

[0882] [Evaluation of Exposure Sensitivity]

[0883] -Formation of photocurable films-

[0884] In each embodiment and comparative example, each photocurable resin composition or comparative composition was applied (coated) onto a silicon wafer in a layered manner by spin coating, thereby forming a resin composition film.

[0885] In each embodiment and comparative example, a silicon wafer to which the obtained resin composition film was applied was dried on a heating plate at 100°C for 2 minutes, thereby forming a photocurable film of the thickness described in the “Film Thickness (μm)” column of Table 5 or Table 6 on the silicon wafer.

[0886] -First Exposure Process-

[0887] The first exposure process of the above-mentioned photocurable film is carried out by the following method.

[0888] In the example where "K" is listed in the "Light Source" column of "First Exposure Step" in Table 5 or Table 6, the above-mentioned photocurable film was exposed using a KrF excimer laser with a wavelength of 248 nm.

[0889] In the example where "i" is listed in the "Light Source" column of "First Exposure Step" in Table 5 or Table 6, the above-mentioned photocurable film was exposed using a high-pressure mercury lamp that cut wavelengths other than 365nm (i-rays) through a bandpass filter.

[0890] In the example where "light source" is listed as "h" in the "first exposure step" column of Table 5 or Table 6, the above-mentioned photocurable film was exposed using a high-pressure mercury lamp that cut wavelengths other than 405nm (h-rays) through a bandpass filter.

[0891] All of the above exposures were performed through a binary mask with a 1:1 line and a spatial pattern formed by the lines having a linewidth of 10μm.

[0892] Furthermore, in the evaluation of exposure sensitivity, the exposure amount was not set as the "exposure amount (mJ / cm)" for the "first exposure step" in Table 5 or Table 6. 2 The exposure levels recorded in the ")" column are in the range of 10–100 mJ / cm². 2 Up to 10mJ / cm 2 Ten points were exposed at intervals.

[0893] -Developing Process-

[0894] The photocurable film after the first exposure process described above is subjected to a development process using the following method.

[0895] In the example where the "developer" field of the "developing process" is labeled "A1" after the above exposure, a developer solution (40°C) is used, which is a mixture of isopropanol (IPA) and 3% by mass of trimethylammonium hydroxide aqueous solution (TMAHaq) at a mass ratio of IPA:TMAHaq = 10:90. The exposed photocurable film is developed and then rinsed with pure water for 30 seconds to obtain a developed pattern. The development is performed by ultrasonic treatment for 8 minutes while immersing the photocurable film in the developer solution.

[0896] Following the above exposure, in the "Developer" column of the "Developing Process," the exposed photocurable film is developed using cyclopentanone (25°C), followed by rinsing with PGMEA (propylene glycol methyl ether acetate) for 30 seconds to obtain the developed pattern. This development is performed using a 5-minute spray development process.

[0897] Following the above exposure, in the "Developing Solution" section of the "Developing Process," labeled "A2," a 3% (w / w) trimethylammonium hydroxide aqueous solution (25°C) was used to develop the exposed photocurable film. The film was then rinsed with pure water for 30 seconds to obtain the developed pattern. This development was performed using a 5-minute spray development process.

[0898] -Second Exposure Process-

[0899] The photocurable film after the above developing process is subjected to a second exposure process using the following method.

[0900] After the above development, in the example where "i" is listed in the "Light Source" column of "Second Exposure Step" in Table 5 or Table 6, a high-pressure mercury lamp with wavelengths other than 365nm (i-rays) cut off by a bandpass filter is used to expose the entire developed pattern. The exposure temperature is set to the temperature listed in the "Exposure Temperature (°C)" column of "Second Exposure Step" in Table 5 or 6. The exposure amount is set to the "Exposure Amount (J / cm²)" column of "Second Exposure Step". 2 The exposure count recorded in the column “)”.

[0901] After the above development, in the example where "B" is listed in the "Light Source" column of "Second Exposure Step" in Table 5 or Table 6, a high-pressure mercury lamp is used without a bandpass filter to expose the entire developed pattern. The exposure temperature is set to the temperature listed in the "Exposure Temperature (°C)" column of "Second Exposure Step" in Table 5 or 6. The exposure amount is set to the "Exposure Amount (J / cm²)" column of "Second Exposure Step". 2 The exposure count recorded in the column “)”.

[0902] In the example where the "Light Source" column of "Second Exposure Step" in Table 5 or Table 6 is marked as "-" after the above development, no exposure was performed.

[0903] -Heating Process-

[0904] The pattern after the second exposure process described above is subjected to a heating process using the following method.

[0905] In the example where the "Temperature (°C)" column of the "Heating Process" in Table 5 or Table 6 is marked as "-" after the second exposure process, no heating was performed, and the developed pattern after the second exposure process was set as the pattern.

[0906] In the example where the "Temperature (°C)" column of the "Heating Process" in Table 5 or Table 6 contains a value after the second exposure process, the developed pattern after the second exposure process is heated at the temperature recorded in the "Temperature (°C)" column of the "Heating Process" and the time recorded in the "Time (min)" column of the "Heating Process" is used to set the developed pattern after the second exposure process as a pattern.

[0907] -evaluate-

[0908] In each embodiment or comparative example, the exposure amount in the first exposure step described above was set to 20 mJ / cm², as observed by an optical microscope. 2 or 100mJ / cm 2 The obtained patterns were evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Exposure Sensitivity Evaluation" column of Table 5 or Table 6. The less exposure required to form a pattern, the better the exposure sensitivity.

[0909] <<Evaluation Criteria>>

[0910] A: Set the exposure level in the first exposure step to 10mJ / cm². 2 or 20mJ / cm 2 In this case, lines and spatial patterns are formed with an exposure of at least one point.

[0911] B: Set the exposure level in the first exposure step to 20mJ / cm². 2 In the following cases, no line and spatial patterns are formed, but the exposure is set to 30mJ / cm. 2 Above and 100mJ / cm 2 In this case, lines and spatial patterns are formed with an exposure of at least one point.

[0912] C: Set the exposure amount in the first exposure step to the aforementioned 10mJ / cm². 2 ~100mJ / cm 2 No lines or spatial patterns were formed under any exposure level.

[0913] [Evaluation of drug resistance]

[0914] -Formation of photocurable films-

[0915] In each embodiment and comparative example, a photocurable resin composition or a comparative composition was used to form a photocurable film using the same method as the formation of the photocurable film in the above-described evaluation of exposure sensitivity.

[0916] -First Exposure Process-

[0917] In each embodiment and comparative example, full-area exposure was performed without using a mask, and the exposure amount was set to the "exposure amount (mJ / cm²)" of the "first exposure step" in Table 5 or Table 6. 2 In addition to the exposure amount recorded in the column “), the first exposure process is performed on the above-mentioned photocurable film by the same method as the first exposure process in the evaluation of exposure sensitivity described above.

[0918] -Second Exposure Process-

[0919] In each embodiment and comparative example, the photocurable film after the first exposure step was subjected to a second exposure step using the same method as the second exposure step in the evaluation of exposure sensitivity described above.

[0920] In the example where the "Light Source" column of "Second Exposure Step" in Table 5 or Table 6 is marked with "-", the second exposure step was not performed.

[0921] Furthermore, in order to simplify the evaluation of drug resistance, imaging was not performed.

[0922] -Heating Process-

[0923] In each embodiment and comparative example, in the case where the value is recorded in the "Temperature (°C)" column of "Heating Process" in Table 5 or Table 6, the photocurable film after the second exposure process is heated by the same method as the heating process in the above-mentioned exposure sensitivity evaluation, thereby obtaining the resin film.

[0924] In the example where the "Temperature (°C)" column of the "Heating Process" in Table 5 or Table 6 is marked as "-", the heating process was not performed, and the photocurable film after the second exposure process is set as a resin film.

[0925] -evaluate-

[0926] The obtained resin layer was immersed in the following solution under the following conditions, and the dissolution rate was calculated.

[0927] Solution: 3% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution

[0928] Evaluation conditions: The resin layer was immersed in the drug solution at 80℃ for 15 minutes. The film thickness before and after immersion was compared, and the film thickness change rate (%) was calculated using the following formula.

[0929] Film thickness change rate (%) = (Film thickness of resin layer before impregnation - Film thickness of resin layer after impregnation) / Film thickness of resin layer before impregnation × 100

[0930] The evaluation was conducted according to the following criteria, and the results were recorded in the "Drug Resistance Evaluation" column of Table 5 or Table 6. The smaller the film thickness change rate (%), the better the drug resistance.

[0931] <<Evaluation Criteria>>

[0932] A: The above film thickness change rate (%) is less than 20%.

[0933] B: The above film thickness change rate (%) is 20% or more and less than 50%.

[0934] C: The above film thickness change rate (%) is 50% or more.

[0935] [Evaluation of membrane shrinkage rate]

[0936] -Formation of photocurable films-

[0937] In each embodiment and comparative example, a photocurable resin composition or a comparative composition was used to form a photocurable film using the same method as the formation of the photocurable film in the above-described evaluation of exposure sensitivity.

[0938] -First Exposure Process-

[0939] In each embodiment and comparative example, the exposure amount is set as the "exposure amount (mJ / cm)" of the "first exposure step" in Table 5 or Table 6. 2 In addition to the exposure amount recorded in the column “), the first exposure process is performed on the above-mentioned photocurable film by the same method as the first exposure process in the evaluation of exposure sensitivity described above.

[0940] -Developing Process-

[0941] In each embodiment and comparative example, the photocurable film after the first exposure step was subjected to a development step using the same method as the development step in the evaluation of exposure sensitivity described above, thereby obtaining a developed pattern.

[0942] -Second Exposure Process-

[0943] In each embodiment and comparative example, the photocurable film after the development process was subjected to a second exposure process using the same method as the second exposure process in the evaluation of exposure sensitivity described above.

[0944] In the example where the "Light Source" column of "Second Exposure Step" in Table 5 or Table 6 is marked with "-", the second exposure step was not performed.

[0945] -Heating Process-

[0946] In each embodiment and comparative example, in the case where the value is recorded in the "Temperature (°C)" column of "Heating Process" in Table 5 or Table 6, the photocurable film after the second exposure process is heated by the same method as the heating process in the above-mentioned exposure sensitivity evaluation, thereby obtaining the pattern.

[0947] In the example where the "Temperature (°C)" column of the "Heating Process" in Table 5 or Table 6 is marked as "-", the heating process was not performed, and the photocurable film after the second exposure process was set as a pattern.

[0948] -evaluate-

[0949] The film thickness (μm) of the developed pattern and the film thickness (μm) of the obtained pattern were measured respectively, and the shrinkage rate was calculated using the following formula.

[0950] Shrinkage rate (%) = (film thickness of developed pattern - film thickness of obtained pattern (μm)) / film thickness of developed pattern (μm) × 100

[0951] The evaluation was conducted according to the following evaluation criteria, and the results were recorded in the "Film Shrinkage Rate Evaluation" column of Table 5 or Table 6. The lower the shrinkage rate (%), the more it inhibits the shrinkage of the developed pattern.

[0952] <<Evaluation Criteria>>

[0953] A: The shrinkage rate (%) mentioned above is less than 10%.

[0954] B: The shrinkage rate (%) mentioned above is 10% or more but less than 20%.

[0955] C: The above shrinkage rate (%) is 20% or more.

[0956] [Evaluation of cyclization rate]

[0957] -Formation of photocurable film ~ Heating process-

[0958] Using the same method as the above-mentioned evaluation of film shrinkage, the formation of a photocurable film, the first exposure step, the development step, the second exposure step, and the heating step were performed sequentially to obtain a pattern.

[0959] -evaluate-

[0960] The FTIR spectra of the obtained patterns were measured, and the cyclization rate was calculated.

[0961] The Horiba FT-210, manufactured by Horiba Corporation, was used as the measuring instrument for FTIR spectroscopy.

[0962] In examples where polymers A-1, B-1, A-2, B-2, D, or E are used as resins, the CN absorption (1376 cm⁻¹) of the imide groups of samples from which the photocurable films used in each example and comparative example were heated at 350°C for 60 minutes before the first exposure step was measured. -1 ( ) is used as a reference sample. Heating is performed on a heated plate. After the above determination, the cyclization rate (%) is calculated using the following formula.

[0963] Circulation rate (%) = the number of elements present in the obtained pattern at 1376 cm⁻¹ -1 The peak intensity of the peak / present in the sample heated at 350℃ for 60 minutes at 1376 cm⁻¹ -1 Peak intensity × 100

[0964] As an example of using polymer C as the resin, the absorption peak of the benzoxazole ring (1554 cm⁻¹) of the sample of the photocurable film used in each example and comparative example before the first exposure process was heated at 350°C for 60 minutes. -1 ( ) is used as a reference sample. Heating is performed on a heated plate. After the above determination, the cyclization rate (%) is calculated using the following formula.

[0965] Circulation rate (%) = the number of elements present in the obtained pattern at 1554 cm⁻¹ -1 The peak intensity of the peak / present in the sample heated at 350℃ for 60 minutes at 1554 cm⁻¹ -1 Peak intensity × 100

[0966] The evaluation is conducted according to the following evaluation criteria, and the evaluation results are recorded in the "Cycloning Rate Evaluation" column of Table 5 or Table 6. The higher the cyclization rate (%), the more cyclization is required.

[0967] <<Evaluation Criteria>>

[0968] A: The cyclization rate (%) is above 95%.

[0969] B: The above cyclization rate (%) is 70% or higher and less than 95%.

[0970] C: The above cyclization rate (%) is less than 70%.

[0971] [Table 5]

[0972]

[0973] [Table 6]

[0974]

[0975] As can be seen from the above results, compared with Comparative Example 1 or Comparative Example 2, which did not perform the second exposure process and were ringed by heating, the pattern forming method of the present invention forms a pattern that suppresses film thickness shrinkage.

[0976] <Example 101>

[0977] The photocurable resin composition used in Example 2 was applied in a layered manner to the surface of a copper thin layer on a resin substrate with a copper thin layer formed thereon using a spin coating method. After drying at 100°C for 2 minutes, a photocurable film with a thickness of 15 μm was formed. Then, a high-pressure mercury lamp with a filter cutting wavelengths other than 365 nm (i-rays) was used at 400 mJ / cm². 2 Exposure was performed using the specified exposure level. Exposure was performed through a mask (a binary mask with a 1:1 line-to-space pattern and a linewidth of 10 μm). After exposure, the layer was developed with cyclopentanone at 25°C for 60 seconds and rinsed with PGMEA for 20 seconds to obtain the layer pattern.

[0978] Next, using a high-pressure mercury lamp at 10 J / cm 2 The material is fully exposed and cured to the required exposure level, thereby forming an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties.

[0979] Furthermore, the results of manufacturing electronic devices using interlayer insulating films with these rewiring layers confirmed that they functioned normally.

Claims

1. A method for forming a pattern, comprising: The first exposure step involves exposing a portion of the photocurable film formed from the photocurable resin composition. The developing process involves developing the exposed photocurable film with a developing solution to obtain a developed pattern. and The second exposure step involves exposing the developed pattern to obtain the pattern. The photocurable resin composition comprises: A resin selected from at least one of polyimide precursors and polybenzoxazole precursors; A photosensitive compound A that is sensitive to the exposure wavelength in the first exposure step; and Photosensitive compound B, which is sensitive to the exposure wavelength in the second exposure step, The photosensitive compound A is a compound that causes a change in the solubility of the photocurable film relative to the developing solution during the first exposure step. The photosensitive compound A is a photoacid generator, and the photosensitive compound B is a photoalkali generator; or The photosensitive compound A is a photoalkalizing agent, and the photosensitive compound B is a photoacidifying agent; or Both photosensitive compound A and photosensitive compound B are photoalkalizing agents.

2. The pattern forming method according to claim 1, wherein, The photosensitive compound A is a compound that generates acid through the first exposure process.

3. The pattern forming method according to claim 1 or 2, wherein, The photosensitive compound B is a compound that produces an alkali through the second exposure process.

4. The pattern forming method according to claim 1 or 2, wherein, The second exposure step includes exposure with light containing light of a wavelength different from the light used in the first exposure step.

5. The pattern forming method according to claim 1 or 2, wherein, The temperature in the second exposure process is 50℃~200℃.

6. A method for manufacturing a laminate, comprising the pattern forming method according to any one of claims 1 to 5.

7. A method for manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 5 or the method for manufacturing a laminate according to claim 6.

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